Nanowire catalysts and methods for their use and preparation

ABSTRACT

Nanowires useful as heterogeneous catalysts are provided. The nanowire catalysts are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane to C2 hydrocarbons. Related methods for use and manufacture of the same are also disclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/689,611, filed on Nov. 29, 2012, now U.S. Pat. No. 8,962,517, whichclaims the benefit under 35 U.S.C. §119(e) of U.S. Provisional PatentApplication No. 61/564,834, filed on Nov. 29, 2011; Provisional PatentApplication No. 61/564,836, filed on Nov. 29, 2011; and U.S. ProvisionalPatent Application No. 61/651,399, filed on May 24, 2012; each of whichare incorporated herein by reference in their entireties.

STATEMENT REGARDING SEQUENCE LISTING

The Sequence Listing associated with this application is provided intext format in lieu of a paper copy, and is hereby incorporated byreference into the specification. The name of the text file containingthe Sequence Listing 860158_420C1_SEQUENCE_LISTING.txt. The text file is19 KB, was created on Dec. 1, 2014, and is being submittedelectronically via EFS-Web.

BACKGROUND

1. Technical Field

This invention is generally related to novel nanowire catalysts and,more specifically, to nanowires useful as heterogeneous catalysts in avariety of catalytic reactions, such as the oxidative coupling ofmethane to C2 hydrocarbons.

2. Description of the Related Art

Catalysis is the process in which the rate of a chemical reaction iseither increased or decreased by means of a catalyst. Positive catalystsincrease the speed of a chemical reaction, while negative catalysts slowit down. Substances that increase the activity of a catalyst arereferred to as promoters or activators, and substances that deactivate acatalyst are referred to as catalytic poisons or deactivators. Unlikeother reagents, a catalyst is not consumed by the chemical reaction, butinstead participates in multiple chemical transformations. In the caseof positive catalysts, the catalytic reaction generally has a lowerrate-limiting free energy change to the transition state than thecorresponding uncatalyzed reaction, resulting in an increased reactionrate at the same temperature. Thus, at a given temperature, a positivecatalyst tends to increase the yield of desired product while decreasingthe yield of undesired side products. Although catalysts are notconsumed by the reaction itself, they may be inhibited, deactivated ordestroyed by secondary processes, resulting in loss of catalyticactivity.

Catalysts are generally characterized as either heterogeneous orhomogeneous. Heterogeneous catalysts exist in a different phase than thereactants (e.g. a solid metal catalyst and gas phase reactants), and thecatalytic reaction generally occurs on the surface of the heterogeneouscatalyst. Thus, for the catalytic reaction to occur, the reactants mustdiffuse to and/or adsorb onto the catalyst surface. This transport andadsorption of reactants is often the rate limiting step in aheterogeneous catalysis reaction. Heterogeneous catalysts are alsogenerally easily separable from the reaction mixture by commontechniques such as filtration or distillation.

In contrast to a heterogeneous catalyst, a homogenous catalyst exists inthe same phase as the reactants (e.g., a soluble organometallic catalystand solvent-dissolved reactants). Accordingly, reactions catalyzed by ahomogeneous catalyst are controlled by different kinetics than aheterogeneously catalyzed reaction. In addition, homogeneous catalystscan be difficult to separate from the reaction mixture.

While catalysis is involved in any number of technologies, oneparticular area of importance is the petrochemical industry. At thefoundation of the modern petrochemical industry is the energy-intensiveendothermic steam cracking of crude oil. Cracking is used to producenearly all the fundamental chemical intermediates in use today. Theamount of oil used for cracking and the volume of green house gases(GHG) emitted in the process are quite large: cracking consumes nearly10% of the total oil extracted globally and produces 200M metric tons ofCO₂ equivalent every year (Ren, T, Patel, M. Res. Conserv. Recycl.53:513, 2009). There remains a significant need in this field for newtechnology directed to the conversion of unreactive petrochemicalfeedstocks (e.g. paraffins, methane, ethane, etc.) into reactivechemical intermediates (e.g. olefins), particularly with regard tohighly selective heterogeneous catalysts for the direct oxidation ofhydrocarbons.

While there are multistep paths to convert methane to certain specificchemicals using first; high temperature steam reforming to syngas (amixture of H₂ and CO), followed by stochiometry adjustment andconversion to either methanol or, via the Fischer-Tropsch (F-T)synthesis, to liquid hydrocarbon fuels such as diesel or gasoline, thisdoes not allow for the formation of certain high value chemicalintermediates. This multi-step indirect method also requires a largecapital investment in facilities and is expensive to operate, in partdue to the energy intensive endothermic reforming step. (For instance,in methane reforming, nearly 40% of methane is consumed as fuel for thereaction.) It is also inefficient in that a substantial part of thecarbon fed into the process ends up as the GHG CO₂, both directly fromthe reaction and indirectly by burning fossil fuels to heat thereaction. Thus, to better exploit the natural gas resource, directmethods that are more efficient, economical and environmentallyresponsible are required.

One of the reactions for direct natural gas activation and itsconversion into a useful high value chemical, is the oxidative couplingof methane (“OCM”) to ethylene: 2CH₄+O₂→C₂H₄+2H₂O. See, e.g., Zhang, Q.,Journal of Natural Gas Chem., 12:81, 2003; Olah, G. “HydrocarbonChemistry”, Ed. 2, John Wiley & Sons (2003). This reaction is exothermic(ΔH=−67 kcals/mole) and has typically been shown to occur at very hightemperatures (>700° C.). Although the detailed reaction mechanism is notfully characterized, experimental evidence suggests that free radicalchemistry is involved. (Lunsford, J. Chem. Soc., Chem. Comm., 1991; H.Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the reaction,methane (CH₄) is activated on the catalyst surface, forming methylradicals which then couple in the gas phase to form ethane (C₂H₆),followed by dehydrogenation to ethylene (C₂H₄). Several catalysts haveshown activity for OCM, including various forms of iron oxide, V₂O₅,MoO₃, Co₃O₄, Pt—Rh, Li/ZrO₂, Ag—Au, Au/Co₃O₄, Co/Mn, CeO₂, MgO, La₂O₃,Mn₃O₄, Na₂WO₄, MnO, ZnO, and combinations thereof, on various supports.A number of doping elements have also proven to be useful in combinationwith the above catalysts.

Since the OCM reaction was first reported over thirty years ago, it hasbeen the target of intense scientific and commercial interest, but thefundamental limitations of the conventional approach to C—H bondactivation appear to limit the yield of this attractive reaction.Specifically, numerous publications from industrial and academic labshave consistently demonstrated characteristic performance of highselectivity at low conversion of methane, or low selectivity at highconversion (J. A. Labinger, Cat. Lett., 1:371, 1988). Limited by thisconversion/selectivity threshold, no OCM catalyst has been able toexceed 20-25% combined C₂ yield (i.e. ethane and ethylene), and moreimportantly, all such reported yields operate at extremely hightemperatures (>800 C).

In this regard, it is believed that the low yield of desired products(i.e. C₂H₄ and C₂H₆) is caused by the unique homogeneous/heterogeneousnature of the reaction. Specifically, due to the high reactiontemperature, a majority of methyl radicals escape the catalyst surfaceand enter the gas phase. There, in the presence of oxygen and hydrogen,multiple side reactions are known to take place (J. A. Labinger, Cat.Lett., 1:371, 1988). The non-selective over-oxidation of hydrocarbons toCO and CO₂ (e.g., complete oxidation) is the principal competing fastside reaction. Other undesirable products (e.g. methanol, formaldehyde)have also been observed and rapidly react to form CO and CO₂.

In order to result in a commercially viable OCM process, a catalystoptimized for the activation of the C—H bond of methane at lowertemperatures (e.g. 500-700° C.), higher activities and higher pressuresare required. While the above discussion has focused on the OCMreaction, numerous other catalytic reactions (as discussed in greaterdetail below) would significantly benefit from catalytic optimization.Accordingly, there remains a need in the art for improved catalysts and,more specifically, a need for novel approaches to catalyst design forimproving the yield of, for example, the OCM reaction and othercatalyzed reactions. The present invention fulfills these needs andprovides further related advantages.

BRIEF SUMMARY

In brief, nanowires and related methods are disclosed. The nanowiresfind utility in any number of applications, including use asheterogeneous catalysts in petrochemical processes, such as OCM. In oneembodiment, the disclosure provides a catalytic nanowire comprising acombination of at least four different doping elements, wherein thedoping elements are selected from a metal element, a semi-metal elementand a non-metal element

In other embodiments, the present disclosure is directed to a catalyticnanowire comprising at least two different doping elements, wherein thedoping elements are selected from a metal element, a semi-metal elementand a non-metal element, and wherein at least one of the doping elementsis K, Sc, Ti, V, Nb, Ru, Os, Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy, Ho,Er, Tm, Lu or an element selected from any of groups 6, 7, 10, 11, 14,15 or 17.

In yet another aspect, the present disclosure provides a catalyticnanowire comprising at least one of the following dopant combinations:Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K,Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K,Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S,Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf,Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au,Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr,Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li,La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag,Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm,Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs,In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn,Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In still other embodiments, the disclosure provides a catalytic nanowirecomprising Ln1_(4-x)Ln2_(x)O₆ and a dopant comprising a metal element, asemi-metal element, a non-metal element or combinations thereof, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4.

In other embodiments, the disclosure provides a nanowire comprising amixed oxide of Y—La, Zr—La, Pr—La, Ce—La or combinations thereof and atleast one dopant selected from a metal element, a semi-metal element anda non-metal element.

In still other embodiments, the invention provides a catalytic nanowirecomprising a mixed oxide of a rare earth element and a Group 13 element,wherein the catalytic nanowire further comprises one or more Group 2elements.

The disclosure is also directed to a catalytic nanowire, wherein thesingle pass methane conversion in an OCM reaction catalyzed by thenanowire is greater than 20%.

In still other embodiments the disclosure provides a catalytic nanowirehaving a C2 selectivity of greater than 10% in the OCM reaction when theOCM reaction is performed with an oxygen source other than air or O₂.For example the catalytic nanowire may have activity in the OCM reactionin the presence of CO₂, H₂O, SO₂, SO₃ or combinations thereof. In someembodiments of the foregoing, the catalytic nanowire comprisesLa₂O₃/ZnO, CeO₂/ZnO, CaO/ZnO, CaO/CeO₂, CaO/Cr₂O₃, CaO/MnO₂, SrO/ZnO,SrO/CeO₂, SrO/Cr₂O₃, SrO/MnO₂, SrCO₃/MnO₂, BaO/ZnO, BaO/CeO₂, BaO/Cr₂O₃,BaO/MnO₂, CaO/MnO/CeO₂, Na₂WO₄/Mn/SiO₂, Pr₂O₃, Tb₂O₃ or combinationsthereof.

In yet other embodiments of any of the foregoing catalytic nanowires,the catalytic nanowire is polycrystalline and has a ratio of effectivelength to actual length of less than one and an aspect ratio of greaterthan ten as measured by TEM in bright field mode at 5 keV, wherein thecatalytic nanowire comprises one or more elements from any of Groups 1through 7, lanthanides, actinides or combinations thereof.

In yet other embodiments of any of the foregoing catalytic nanowires,the catalytic nanowire has a bent morphology, and in other embodimentsthe catalytic nanowire has a straight morphology. In yet otherembodiments of any of the foregoing catalytic nanowires, the catalyticnanowire comprises a metal oxide, metal oxy-hydroxide, a metaloxycarbonate, a metal carbonate or combinations thereof, for example insome embodiments the catalytic nanowire comprises a metal oxide.

The present disclosure also provides a catalytic material comprising aplurality of catalytic nanowires in combination with a diluent orsupport, wherein the diluent or support comprises an alkaline earthmetal compound. In some embodiments, the alkaline earth metal compoundis MgO, MgCO₃, MgSO₄, Mg₃(PO₄)₂, MgAl₂O₄, CaO, CaCO₃, CaSO₄, Ca₃(PO₄)₂,CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄, BaO, BaCO₃, BaSO₄,Ba₃(PO₄)₂, BaAl₂O₄ or combinations thereof. For example, in someembodiments the alkaline earth metal compound is MgO, CaO, SrO, MgCO₃,CaCO₃, SrCO₃ or combinations thereof. In other embodiments, thecatalytic material is in the form of a pressed pellet, extrudate ormonolith structure.

In other embodiments, the disclosure relates to a catalytic materialcomprising a plurality of catalytic nanowires and a sacrificial binder,and in other embodiments the disclosure is directed to a catalyticmaterial in the form of a pressed pellet (e.g., pressure treated),wherein the catalytic material comprises a plurality of catalyticnanowires and substantially no binder material.

In other embodiments, the disclosure provides a catalytic material inthe form of a pressed pellet or extrudate, wherein the catalyticmaterial comprises a plurality of catalytic nanowires and pores greaterthan 20 nm in diameter. For example, in some embodiments the catalyticmaterial is in the form of a pellet, and in other embodiments, thecatalytic material is in the form of an extrudate.

In still other embodiments of the present disclosure, a catalyticmaterial comprising a plurality of catalytic nanowires supported on astructured support is provided. For example, the structured support maycomprise a foam, foil or honeycomb structure. In other embodiments, thestructured support comprises silicon carbide or alumina, and in stillother embodiments the structured support comprises a metal foam, siliconcarbide or alumina foams, corrugated metal foil arranged to form channelarrays or extruded ceramic honeycomb.

Other embodiments provide a catalytic material comprising a catalyticnanowire, wherein the catalytic material is in contact with a reactor.For example, in some embodiments the reactor is used for performing OCM,and in other embodiments the catalytic material comprises siliconcarbide. In further embodiments the reactor is a fixed bed reactor, andin other examples the reactor comprises an inner diameter of at least 1inch.

In another embodiment, the disclosure provides a catalytic materialcomprising at least one O₂-OCM catalyst and at least one CO₂-OCMcatalyst. For example in some aspects at least one of the O₂-OCMcatalyst or the CO₂-OCM catalyst is a catalytic nanowire.

In another embodiment, the disclosure provides a catalytic materialcomprising at least one O₂-OCM catalyst and at least one CO₂-ODHcatalyst. For example in some aspects at least one of the O₂-OCMcatalyst or the CO₂-ODH catalyst is a catalytic nanowire.

In other embodiments of any of the foregoing catalytic materials, thecatalytic material comprises any of the catalytic nanowires disclosedherein.

Other embodiments of the present disclosure include a method forpreparing a catalytic material, the method comprising admixing aplurality of catalytic nanowires with a sacrificial binder and removingthe sacrificial binder to obtain a catalytic material comprisingsubstantially no binder material and having an increased microporositycompared a to catalytic material prepared without the sacrificialbinder. For example, the catalytic material may be any of the foregoingcatalytic materials.

In still other embodiments, the disclosure is directed to a method forpurifying a phage solution, the method comprising:

a) a microfiltration step comprising filtering a phage solution througha membrane comprising pores ranging from 0.1 to 3 μm to obtain amicrofiltration retentate and a microfiltration permeate; and

b) an ultrafiltration step comprising filtering the microfiltrationpermeate through a membrane comprising pores ranging from 1 to 1000 kDaand recovering an ultrafiltration retentate comprising a purified phagesolution.

In some embodiments, the ultrafiltration step is performed usingtangential flow filtration. In other embodiments, the method furthercomprises diafiltrating the purified phage solution to exchange mediafor buffer solution.

In some embodiments, the microfiltration step and the ultrafiltrationstep are performed using tangential flow filtration, while in otherembodiments the microfiltration step is performed using depthfiltration.

In other embodiments, the disclosure provides a method for preparing acatalytic nanowire comprising a metal oxide, a metal oxy-hydroxide, ametal oxycarbonate or a metal carbonate, the method comprising:

a) providing a solution comprising a plurality of biological templates;

(b) introducing at least one metal ion and at least one anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire comprising a plurality of metalsalts (M_(m)X_(n)Z_(p)) on the template; and

(c) converting the nanowire (M_(m)X_(n)Z_(p)) to a metal oxide nanowirecomprising a plurality of metal oxides (M_(x)O_(y)), metaloxy-hydroxides (M_(x)O_(y)OH_(z)), metal oxycarbonates(M_(x)O_(y)(CO₃)_(z)), metal carbonate (M_(x)(CO₃)_(y)) or combinationsthereof

wherein:

M is, at each occurrence, independently a metal element from any ofGroups 1 through 7, lanthanides or actinides;

X is, at each occurrence, independently hydroxides, carbonates,bicarbonates, phosphates, hydrogenphosphates, dihydrogenphosphates,sulfates, nitrates or oxalates;

Z is O;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In yet other embodiments, the disclosure provides a method for preparingmetal oxide, metal oxy-hydroxide, metal oxycarbonate or metal carbonatecatalytic nanowires in a core/shell structure, the method comprising:

(a) providing a solution that includes a plurality of biologicaltemplates;

(b) introducing a first metal ion and a first anion to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a first nanowire (M1_(m1)X1_(n1) Z_(p1)) on the template; and

(c) introducing a second metal ion and optionally a second anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a second nanowire (M2_(m2)X2_(n2) Z_(p2)) onthe first nanowire (M1_(m1)X1_(n1) Z_(p1));

(d) converting the first nanowire (M1_(m1)X1_(n1) Z_(p1)) and the secondnanowire (M2_(m2)X2_(n2) Z_(p2)) to the respective metal oxide nanowires(M1_(x1)O_(y1)) and (M2_(x2)O_(y2)), the respective metal oxy-hydroxidenanowires (M1_(x1)O_(y1)OH_(z1)) and (M2_(x2)O_(y2)OH_(z2)) therespective metal oxycarbonate nanowires (M1_(x1)O_(y1)(CO₃)_(z1)) and(M2_(x2)O_(y2)(CO₃)_(z2)) or the respective metal carbonate nanowires(M1_(x1)(CO₃)_(y1)) and (M2_(x2)(CO₃)_(y2)),

wherein:

M1 and M2 are the same or different and independently selected from ametal element;

X1 and X2 are the same or different and independently hydroxides,carbonates, bicarbonates, phosphates, hydrogenphosphates,dihydrogenphosphates, sulfates, nitrates or oxalates;

Z is O;

n1, m1n2, m2, x1, y1, z1, x2, y2 and z2 are each independently a numberfrom 1 to 100; and

p1 and p2 are independently a number from 0 to 100.

In still other embodiments, the disclosure provides a method forpreparing a catalytic nanowire, the method comprising treating at leastone metal compound with an ammonium salt having the formula NR₄X,wherein each R is independently H, alkyl, alkenyl, alkynyl or aryl, andX is an anion. For example, in some embodiments X is phosphate,hydrogenphosphage, dihydrogenphosphate, metatungstate, tungstate,molybdate, bicarbonate sulfate, nitrate or acetate.

In other embodiments of the foregoing method, the method comprisestreating two or more different metal compounds with the ammonium saltand the nanowire comprises two or more different metals. In otherembodiments, the nanowire comprises a mixed metal oxide, metaloxyhalide, metal oxynitrate or metal sulfate, and in other aspects theammonium salt is contacted with the metal compound in solution or in thesolid state.

In still other embodiments of the foregoing method, the method furthercomprises treating the at least one metal compound with the ammoniumsalt in the presence of at least one doping element, and the nanowirecomprises the least one doping element. In other embodiments, the atleast one metal compound is an oxide of a lanthanide element. In stillother embodiments, R is methyl, ethyl, propyl, isopropyl, butyl,tert-butyl, pentenyl, cyclohexyl, phenyl, tolyl, benzyl, hexynyl, octyl,octenyl, octynyl, dodecyl, cetyl, oleyl or stearyl.

In other embodiments of the foregoing method, the ammonium salt isammonium chloride, dimethylammonium chloride, methylammonium chloride,ammonium acetate, ammonium nitrate, dimethylammonium nitrate,methylammonium nitrate or cetyl trimethylammonium bromide (CTAB), whilein other embodiments the method further comprises treating the metaloxide and ammonium salt at temperatures ranging from 0° C. to refluxtemperature in an aqueous solvent for a time sufficient to produce thenanowires. Other examples comprise heating the metal oxide and ammoniumsalt under hydrothermal conditions at temperatures ranging from refluxtemperature to 300° C. at atmospheric pressure.

In another embodiment, the disclosure provides a method for theoxidative coupling of methane, the method comprising converting methaneto one or more C2 hydrocarbons in the presence of a catalytic material,wherein the catalytic material comprises at least one O₂-OCM catalystand at least one CO₂-OCM catalyst. In some embodiments, at least one ofthe O₂-OCM catalyst or the CO₂-OCM catalyst is a catalytic nanowire, forexample any of the nanowires disclosed herein. In some embodiments, thecatalytic material comprises a bed of alternating layers of O₂-OCMcatalysts and CO₂-OCM catalysts, while in other embodiments thecatalytic material comprises a homogeneous mixture of O₂-OCM catalystsand CO₂-OCM catalysts.

In yet more embodiments, the disclosure provides a method for thepreparation of ethane, ethylene or combinations thereof, the methodcomprising converting methane to ethane, ethylene or combinationsthereof in the presence of a catalytic material, wherein the catalyticmaterial comprises at least one O₂-OCM catalyst and at least one CO₂-ODHcatalyst. For example, in some embodiments at least one of the O₂-OCMcatalyst or the CO₂-OCM catalyst is a catalytic nanowire, for exampleany of the catalytic nanowires disclosed herein, such as a metal oxide,metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate nanowireor combinations thereof.

These and other aspects of the invention will be apparent upon referenceto the following detailed description. To this end, various referencesare set forth herein which describe in more detail certain backgroundinformation, procedures, compounds and/or compositions, and are eachhereby incorporated by reference in their entirety.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, the sizes and relative positions of elements in thedrawings are not necessarily drawn to scale. For example, the variouselements and angles are not drawn to scale, and some of these elementsare arbitrarily enlarged and positioned to improve drawing legibility.Further, the particular shapes of the elements as drawn are not intendedto convey any information regarding the actual shape of the particularelements, and have been selected solely for ease of recognition in thedrawings.

FIG. 1 schematically depicts a first part of an OCM reaction at thesurface of a metal oxide catalyst.

FIG. 2 shows a high throughput work flow for synthetically generatingand testing libraries of nanowires.

FIGS. 3A and 3B illustrate a nanowire in one embodiment.

FIGS. 4A and 4B illustrate a nanowire in a different embodiment.

FIGS. 5A and 5B illustrate a plurality of nanowires.

FIG. 6 illustrates a filamentous bacteriophage.

FIG. 7 is a flow chart of an exemplary nucleation process for forming ametal oxide nanowire.

FIG. 8 is a flow chart of an exemplary sequential nucleation process forforming a nanowire in a core/shell configuration.

FIG. 9 schematically depicts a carbon dioxide reforming reaction on acatalytic surface.

FIG. 10 is a flow chart for data collection and processing in evaluatingcatalytic performance.

FIG. 11 illustrates a number of downstream products of ethylene.

FIG. 12 depicts a representative process for preparing a lithium dopedMgO nanowire.

FIG. 13 presents the X-ray diffraction patterns of Mg(OH)2 nanowires andMgO nanowires.

FIG. 14 shows a number of MgO nanowires each synthesized in the presenceof a different phage sequence.

FIG. 15 depicts a representative process for growing a core/shellstructure of ZrO₂/La₂O₃ nanowires with Strontium dopant.

FIG. 16 is a gas chromatograph showing the formation of OCM products at700° C. when passed over a Sr doped La₂O₃ nanowire.

FIGS. 17A-17C are graphs showing methane conversion, C2 selectivity, andC2 yield, in an OCM reaction catalyzed by Sr doped La₂O₃ nanowires vs.the corresponding bulk material in the same reaction temperature range.

FIGS. 18A-18B are graphs showing the comparative results of C2selectivities in an OCM reaction catalyzed by Sr doped La₂O₃ nanowirecatalysts prepared by different synthetic conditions.

FIG. 19 is a graph comparing ethane and propane conversions in ODHreactions catalyzed by either Li doped MgO phage-based nanowires or Lidoped MgO bulk catalyst.

FIG. 20 is a TEM image showing La₂O₃ nanowires prepared undernon-template-directed conditions.

FIG. 21 depicts OCM and ethylene oligomerization modules.

FIG. 22 shows methane conversion, C2 selectivity and C2 yield in areaction catalyzed by representative nanowires.

FIG. 23 shows methane conversion, C2 selectivity and C2 yield in areaction catalyzed by representative nanowires.

FIG. 24 is a graph showing methane conversion, C2 selectivity and C2yield in a reaction catalyzed by representative nanowires.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments.However, one skilled in the art will understand that the invention maybe practiced without these details. In other instances, well-knownstructures have not been shown or described in detail to avoidunnecessarily obscuring descriptions of the embodiments. Unless thecontext requires otherwise, throughout the specification and claimswhich follow, the word “comprise” and variations thereof, such as,“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.” Further, headingsprovided herein are for convenience only and do not interpret the scopeor meaning of the claimed invention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment. Thus, the appearances of the phrases “in one embodiment” or“in an embodiment” in various places throughout this specification arenot necessarily all referring to the same embodiment. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments. Also, as used in thisspecification and the appended claims, the singular forms “a,” “an,” and“the” include plural referents unless the content clearly dictatesotherwise. It should also be noted that the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As discussed above, heterogeneous catalysis takes place between severalphases. Generally, the catalyst is a solid, the reactants are gases orliquids and the products are gases or liquids. Thus, a heterogeneouscatalyst provides a surface that has multiple active sites foradsorption of one more gas or liquid reactants. Once adsorbed, certainbonds within the reactant molecules are weakened and dissociate,creating reactive fragments of the reactants, e.g., in free radicalforms. One or more products are generated as new bonds between theresulting reactive fragments form, in part, due to their proximity toeach other on the catalytic surface.

As an example, FIG. 1 shows schematically the first part of an OCMreaction that takes place on the surface of a metal oxide catalyst 10which is followed by methyl radical coupling in the gas phase. A crystallattice structure of metal atoms 14 and oxygen atoms 20 are shown, withan optional dopant 24 incorporated into the lattice structure. In thisreaction, a methane molecule 28 comes into contact with an active site(e.g., surface oxygen 30) and becomes activated when a hydrogen atom 34dissociates from the methane molecule 28. As a result, a methyl radical40 is generated on or near the catalytic surface. Two methyl radicalsthus generated can couple in the gas phase to create ethane and/orethylene, which are collectively referred to as the “C2” couplingproducts.

It is generally recognized that the catalytic properties of a catalyststrongly correlate to its surface morphology. Typically, the surfacemorphology can be defined by geometric parameters such as: (1) thenumber of surface atoms (e.g., the surface oxygen of FIG. 1) thatcoordinate to the reactant; and (2) the degree of coordinativeunsaturation of the surface atoms, which is the coordination number ofthe surface atoms with their neighboring atoms. For example, thereactivity of a surface atom decreases with decreasing coordinativeunsaturation. For example, for the dense surfaces of a face-centeredcrystal, a surface atom with 9 surface atom neighbors will have adifferent reactivity than one with 8 neighbors. Additional surfacecharacteristics that may contribute to the catalytic properties include,for example, crystal dimensions, lattice distortion, surfacereconstructions, defects, grain boundaries, and the like. See, e.g., VanSanten R. A. et al New Trends in Materials Chemistry 345-363 (1997).

Catalysts in nano-size dimensions have substantially increased surfaceareas compared to their counterpart bulk materials. The catalyticproperties are expected to be enhanced as more surface active sites areexposed to the reactants. Typically in traditional preparations, atop-down approach (e.g., milling) is adopted to reduce the size of thebulk material. However, the surface morphologies of such catalystsremain largely the same as those of the parent bulk material.

Various embodiments described herein are directed to nanowires withcontrollable or tunable surface morphologies. In particular, nanowiressynthesized by a “bottom up” approach, by which inorganicpolycrystalline nanowires are nucleated from solution phase in thepresence of a template, e.g., a linear or anisotropic shaped biologicaltemplate. By varying the synthetic conditions, nanowires havingdifferent compositions and/or different surface morphologies aregenerated.

In contrast to a bulk catalyst of a given elemental composition, whichis likely to have a particular corresponding surface morphology, diversenanowires with different surface morphologies can be generated despitehaving the same elemental composition. In this way, morphologicallydiverse nanowires can be created and screened according to theircatalytic activity and performance parameters in any given catalyticreaction. Advantageously, the nanowires disclosed herein and methods ofproducing the same have general applicability to a wide variety ofheterogeneous catalyses, including without limitation: oxidativecoupling of methane (e.g., FIG. 1), oxidative dehydrogenation of alkanesto their corresponding alkenes, selective oxidation of alkanes toalkenes and alkynes, oxidation of carbon monoxide, dry reforming ofmethane, selective oxidation of aromatics, Fischer-Tropsch reaction,hydrocarbon cracking and the like.

FIG. 2 schematically shows a high throughput work flow for syntheticallygenerating libraries of morphologically or compositionally diversenanowires and screening for their catalytic properties. An initial phaseof the work flow involves a primary screening, which is designed tobroadly and efficiently screen a large and diverse set of nanowires thatlogically could perform the desired catalytic transformation. Forexample, certain doped bulk metal oxides (e.g., Li/MgO and Sr/La₂O₃) areknown catalysts for the OCM reaction. Therefore, nanowires of variousmetal oxide compositions and/or surface morphologies can be prepared andevaluated for their catalytic performances in an OCM reaction.

More specifically, the work flow 100 begins with designing syntheticexperiments based on solution phase template formations (block 110). Thesynthesis, subsequent treatments and screenings can be manual orautomated. As will be discussed in more detail herein, by varying thesynthetic conditions, nanowires can be prepared with various surfacemorphologies and/or compositions in respective microwells (block 114).The nanowires are subsequently calcined and then optionally doped (block120). Optionally, the doped and calcined nanowires are further mixedwith a catalyst support (block 122). Beyond the optional support step,all subsequent steps are carried out in a “wafer” format, in whichnanowire catalysts are deposited in a quartz wafer that has been etchedto create an ordered array of microwells. Each microwell is aself-contained reactor, in which independently variable processingconditions can be designed to include, without limitation, respectivechoices of elemental compositions, catalyst support, reactionprecursors, templates, reaction durations, pH values, temperatures,ratio between reactants, gas flows, and calcining conditions (block124). Due to design constraints of some wafers, in some embodimentscalcining and other temperature variables are identical in allmicrowells. A wafer map 130 can be created to correlate the processingconditions to the nanowire in each microwell. A library of diversenanowires can be generated in which each library member corresponds to aparticular set of processing conditions and corresponding compositionaland/or morphological characteristics.

Nanowires obtained under various synthetic conditions are thereafterdeposited in respective microwells of a wafer (140) for evaluating theirrespective catalytic properties in a given reaction (blocks 132 and134). The catalytic performance of each library member can be screenedserially by several known primary screening technologies, includingscanning mass spectroscopy (SMS) (Symyx Technologies Inc., Santa Clara,Calif.). The screening process is fully automated, and the SMS tool candetermine if a nanowire is catalytically active or not, as well as itsrelative strength as a catalyst at a particular temperature. Typically,the wafer is placed on a motion control stage capable of positioning asingle well below a probe that flows the feed of the starting materialover the nanowire surface and removes reaction products to a massspectrometer and/or other detector technologies (blocks 134 and 140).The individual nanowire is heated to a preset reaction temperature,e.g., using a CO₂ IR laser from the backside of the quartz wafer and anIR camera to monitor temperature and a preset mixture of reactant gases.The SMS tool collects data with regard to the consumption of thereactant(s) and the generation of the product(s) of the catalyticreaction in each well (block 144), and at each temperature and flowrate.

The SMS data obtained as described above provide information on relativecatalytic properties among all the library members (block 150). In orderto obtain more quantitative data on the catalytic properties of thenanowires, possible hits that meet certain criteria are subjected to asecondary screening (block 154). Typically, secondary screeningtechnologies include a single, or alternatively multiple channelfixed-bed or fluidized bed reactors (as described in more detailherein). In parallel reactor systems or multi-channel fixed-bed reactorsystem, a single feed system supplies reactants to a set of flowrestrictors. The flow restrictors divide the flows evenly among parallelreactors. Care is taken to achieve uniform reaction temperature betweenthe reactors such that the various nanowires can be differentiatedsolely based on their catalytic performances. The secondary screeningallows for accurate determination of catalytic properties such asselectivity, yield and conversion (block 160). These results serve as afeedback for designing further nanowire libraries.

Secondary screening is also schematically depicted in FIG. 10, whichdepicts a flow chart for data collection and processing in evaluatingcatalytic performance of catalysts according to the invention.Additional description of SMS tools in a combinatorial approach fordiscovering catalysts can be found in, e.g., Bergh, S. et al. Topics inCatalysts 23:1-4, 2003.

Thus, in accordance with various embodiments described herein,compositional and morphologically diverse nanowires can be rationallysynthesized to meet catalytic performance criteria. These and otheraspects of the present disclosure are described in more detail below.

DEFINITIONS

As used herein, and unless the context dictates otherwise, the followingterms have the meanings as specified below.

“Catalyst” means a substance that alters the rate of a chemicalreaction. A catalyst may either increase the chemical reaction rate(i.e. a “positive catalyst”) or decrease the reaction rate (i.e. a“negative catalyst”). Catalysts participate in a reaction in a cyclicfashion such that the catalyst is cyclically regenerated. “Catalytic”means having the properties of a catalyst.

“Nanoparticle” means a particle having at least one diameter on theorder of nanometers (e.g. between about 1 and 100 nanometers).

“Nanowire” means a nanowire structure having at least one diameter onthe order of nanometers (e.g. between about 1 and 100 nanometers) and anaspect ratio greater than 10:1. The “aspect ratio” of a nanowire is theratio of the actual length (L) of the nanowire to the diameter (D) ofthe nanowire. Aspect ratio is expressed as L:D.

“Polycrystalline nanowire” means a nanowire having multiple crystaldomains. Polycrystalline nanowires generally have different morphologies(e.g. bent vs. straight) as compared to the corresponding“single-crystalline” nanowires.

“Effective length” of a nanowire means the shortest distance between thetwo distal ends of a nanowire as measured by transmission electronmicroscopy (TEM) in bright field mode at 5 keV. “Average effectivelength” refers to the average of the effective lengths of individualnanowires within a plurality of nanowires.

“Actual length” of a nanowire means the distance between the two distalends of a nanowire as traced through the backbone of the nanowire asmeasured by TEM in bright field mode at 5 keV. “Average actual length”refers to the average of the actual lengths of individual nanowireswithin a plurality of nanowires.

The “diameter” of a nanowire is measured in an axis perpendicular to theaxis of the nanowire's actual length (i.e. perpendicular to thenanowires backbone). The diameter of a nanowire will vary from narrow towide as measured at different points along the nanowire backbone. Asused herein, the diameter of a nanowire is the most prevalent (i.e. themode) diameter.

The “ratio of effective length to actual length” is determined bydividing the effective length by the actual length. A nanowire having a“bent morphology” will have a ratio of effective length to actual lengthof less than one as described in more detail herein. A straight nanowirewill have a ratio of effective length to actual length equal to one asdescribed in more detail herein.

“Inorganic” means a substance comprising a metal element or semi-metalelement. In certain embodiments, inorganic refers to a substancecomprising a metal element. An inorganic compound can contain one ormore metals in its elemental state, or more typically, a compound formedby a metal ion (M^(n+), wherein n 1, 2, 3, 4, 5, 6 or 7) and an anion(X^(m−), m is 1, 2, 3 or 4), which balance and neutralize the positivecharges of the metal ion through electrostatic interactions.Non-limiting examples of inorganic compounds include oxides, hydroxides,halides, nitrates, sulfates, carbonates, phosphates, acetates, oxalates,and combinations thereof, of metal elements. Other non-limiting examplesof inorganic compounds include Li₂CO₃, Li₂PO₄, LiOH, Li₂O, LiCl, LiBr,LiI, Li₂C₂O₄, Li₂SO₄, Na₂CO₃, Na₂PO₄, NaOH, Na₂O, NaCl, NaBr, NaI,Na₂C₂O₄, Na₂SO₄, K₂CO₃, K₂PO₄, KOH, K₂O, KCl, KBr, K₁, K₂C₂O₄, K₂SO₄,Cs₂CO₃, CsPO₄, CsOH, Cs₂O, CsCl, CsBr, CsI, CsC₂O₄, CsSO₄, Be(OH)₂,BeCO₃, BePO₄, BeO, BeCl₂, BeBr₂, BeI₂, BeC₂O₄. BeSO₄, Mg(OH)₂, MgCO₃,MgPO₄, MgO, MgCl₂, MgBr₂, MgI₂, MgC₂O₄. MgSO₄, Ca(OH)₂, CaO, CaCO₃,CaPO₄, CaCl₂, CaBr₂, CaI₂, Ca(OH)₂, CaC₂O₄, CaSO₄, Y₂O₃, Y₂(CO₃)₃,Y₂(PO₄)₃, Y(OH)₃, YCl₃, YBr₃, YI₃, Y₂(C₂O₄)₃, Y₂ (SO₄)₃, Zr(OH)₄,Zr(CO₃)₂, Zr(PO₄)₂, ZrO(OH)₂, ZrO2, ZrCl₄, ZrBr₄, ZrI₄, Zr(C₂O₄)₂,Zr(SO₄)₂, Ti(OH)₄, TiO(OH)₂, Ti(CO₃)₂, Ti(PO₄)₂, TiO2, TiCl₄, TiBr₄,TiI₄, Ti(C₂O₄)₂, Ti(SO₄)₂, BaO, Ba(OH)₂, BaCO₃, BaPO₄, BaCl₂, BaBr₂,BaI₂, BaC₂O₄, BaSO₄, La(OH)₃, La₂(CO₃)₃, La₂(PO₄)₃, La₂O₃, LaCl₃, LaBr₃,LaI₃, La₂(C₂O₄)₃, La₂(SO₄)₃, Ce(OH)₄, Ce(CO₃)₂, Ce(PO₄)₂, CeO₂, Ce₂O₃,CeCl₄, CeBr₄, CeI₄, Ce(C₂O₄)₂, Ce(SO₄)₂, ThO₂, Th(CO₃)₂, Th(PO₄)₂,ThCl₄, ThBr₄, ThI₄, Th(OH)₄, Th(C₂O₄)₂, Th(SO₄)₂, Sr(OH)₂, SrCO₃, SrPO₄,SrO, SrCl₂, SrBr₂, SrI₂, SrC₂O₄, SrSO₄, Sm₂O₃, Sm₂(CO₃)₃, Sm₂(PO₄)₃,SmCl₃, SmBr₃, SmI₃, Sm(OH)₃, Sm₂(CO₃)₃, Sm₂(OC₂O₃)₃, Sm₂(SO₄)₃,LiCa₂Bi₃O₄Cl₆, Na₂WO₄, K/SrCoO₃, K/Na/SrCoO₃, Li/SrCoO₃, SrCoO₃,molybdenum oxides, molybdenum hydroxides, molybdenum carbonates,molybdenum phosphates, molybdenum chlorides, molybdenum bromides,molybdenum iodides, molybdenum oxalates, molybdenum sulfates, manganeseoxides, manganese chlorides, manganese bromides, manganese iodides,manganese hydroxides, manganese oxalates, manganese sulfates, manganesetugstates, vanadium oxides, vanadium carbonates, vanadium phosphates,vanadium chlorides, vanadium bromides, vanadium iodides, vanadiumhydroxides, vanadium oxalates, vanadium sulfates, tungsten oxides,tungsten carbonates, tungsten phosphates, tungsten chlorides, tungstenbromides, tungsten iodides, tungsten hydroxides, tungsten oxalates,tungsten sulfates, neodymium oxides, neodymium carbonates, neodymiumphosphates, neodymium chlorides, neodymium bromides, neodymium iodides,neodymium hydroxides, neodymium oxalates, neodymium sulfates, europiumoxides, europium carbonates, europium phosphates, europium chlorides,europium bromides, europium iodides, europium hydroxides, europiumoxalates, europium sulfates rhenium oxides, rhenium carbonates, rheniumphosphates, rhenium chlorides, rhenium bromides, rhenium iodides,rhenium hydroxides, rhenium oxalates, rhenium sulfates, chromium oxides,chromium carbonates, chromium phosphates, chromium chlorides, chromiumbromides, chromium iodides, chromium hydroxides, chromium oxalates,chromium sulfates, potassium molybdenum oxides and the like.

“Salt” means a compound comprising negative and positive ions. Salts aregenerally comprised of cations and counter ions. Under appropriateconditions, e.g., the solution also comprises a template, the metal ion(M^(n+)) and the anion (X^(m−)) bind to the template to inducenucleation and growth of a nanowire of M_(m)X_(n) on the template.“Anion precursor” thus is a compound that comprises an anion and acationic counter ion, which allows the anion (X^(m−)) to dissociate fromthe cationic counter ion in a solution. Specific examples of the metalsalt and anion precursors are described in further detail herein.

“Oxide” refers to a metal compound comprising oxygen. Examples of oxidesinclude, but are not limited to, metal oxides (M_(x)O_(y)), metaloxyhalides (M_(x)O_(y)X_(z)), metal oxynitrates (M_(x)O_(y)(NO₃)_(z)),metal phosphates (M_(x)(PO₄)_(y)), metal oxycarbonates(M_(x)O_(y)(CO₃)_(z)), metal carbonates, metal oxyhydroxides(M_(x)O_(y)(OH)_(z)) and the like, wherein X is independently, at eachoccurrence, fluoro, chloro, bromo or iodo, and x, y and z are numbersfrom 1 to 100.

“Mixed oxide” or “mixed metal oxide” refers to a compound comprising twoor more oxidized metals and oxygen (i.e., M1_(x)M2_(y)O_(z), wherein M1and M2 are the same or different metal elements, O is oxygen and x, yand z are numbers from 1 to 100). A mixed oxide may comprise metalelements in various oxidation states and may comprise more than one typeof metal element. For example, a mixed oxide of manganese and magnesiumcomprises oxidized forms of magnesium and manganese. Each individualmanganese and magnesium atom may or may not have the same oxidationstate. Mixed oxides comprising 2, 3, 4, 5, 6 or more metal elements canbe represented in an analogous manner. Mixed oxides also includeoxy-hydroxides (e.g., M_(x)O_(y)OH_(z), wherein M is a metal element, Ois oxygen, x, y and z are numbers from 1 to 100 and OH is hydroxy).Mixed oxides may be represented herein as M1-M2, wherein M1 and M2 areeach independently a metal element.

“Rare earth oxide” refers to an oxide of an element from group 3,lanthanides or actinides. Rare earth oxides include mixed oxidescontaining a rare earth element. Examples of rare earth oxides include,but are not limited to, La₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃,Pr₂O₃, Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La,Pr—La and Ce—La.

“Crystal domain” means a continuous region over which a substance iscrystalline.

“Single-crystalline nanowires” means a nanowire having a single crystaldomain.

“Template” is any synthetic and/or natural material that provides atleast one nucleation site where ions can nucleate and grow to formnanoparticles. In certain embodiments, the templates can be amulti-molecular biological structure comprising one or morebiomolecules. Typically, the biological template comprises multiplebinding sites that recognize certain ions and allow for the nucleationand growth of the same. Non-limiting examples of biological templatesinclude bacteriophages, amyloid fibers, viruses and capsids.

“Biomolecule” refers to any organic molecule of a biological origin.Biomolecule includes modified and/or degraded molecules of a biologicalorigin. Non-limiting examples of biomolecules include peptides, proteins(including cytokines, growth factors, etc.), nucleic acids,polynucleotides, amino acids, antibodies, enzymes, and single-strandedor double-stranded nucleic acid, including any modified and/or degradedforms thereof.

“Amyloid fibers” refers to proteinaceous filaments of about 1-25 nm indiameter.

A “bacteriophage” or “phage” is any one of a number of viruses thatinfect bacteria. Typically, bacteriophages consist of an outer proteincoat or “major coat protein” enclosing genetic material. A non-limitingexample of a bacteriophage is the M13 bacteriophage. Non-limitingexamples of bacteriophage coat proteins include the pIII, pV, pVIII,etc. protein as described in more detail below.

A “capsid” is the protein shell of a virus. A capsid comprises severaloligomeric structural subunits made of proteins.

“Nucleation” refers to the process of forming a solid from solubilizedparticles, for example forming a nanowire in situ by converting asoluble precursor (e.g. metal and hydroxide ions) into nanocrystals inthe presence of a template.

“Nucleation site” refers to a site on a template, for example abacteriophage, where nucleation of ions may occur. Nucleation sitesinclude, for example, amino acids having carboxylic acid (—COOH), amino(—NH₃ ⁺ or —NH₂), hydroxyl (—OH), and/or thiol (—SH) functional groups.

A “peptide” refers to two or more amino acids joined by peptide (amide)bonds. The amino-acid building blocks (subunits) include naturallyoccurring α-amino acids and/or unnatural amino acids, such asp-aminoacids and homoamino acids. An unnatural amino acid can be a chemicallymodified form of a natural amino acid. Peptides can be comprised of 2 ormore, 5 or more, 10 or more, 20 or more, or 40 or more amino acids.

“Peptide sequence” refers to the sequence of amino acids within apeptide or protein.

“Protein” refers to a natural or engineered macromolecule having aprimary structure characterized by peptide sequences. In addition to theprimary structure, proteins also exhibit secondary and tertiarystructures that determine their final geometric shapes.

“Polynucleotide” means a molecule comprised of two or more nucleotidesconnected via an internucleotide bond (e.g. a phosphate bond).Polynucleotides may be comprised of both ribose and/or deoxy ribosenucleotides. Examples of nucleotides include guanosine, adenosine,thiamine, and cytosine, as well as unnatural analogues thereof.

“Nucleic acid” means a macromolecule comprised of polynucleotides.Nucleic acids may be both single stranded and double stranded, and, likeproteins, can exhibit secondary and tertiary structures that determinetheir final geometric shapes.

“Nucleic acid sequence” of “nucleotide sequence” refers to the sequenceof nucleotides within a polynucleotide or nucleic acid.

“Anisotropic” means having an aspect ratio greater than one.

“Anisotropic biomolecule” means a biomolecule, as defined herein, havingan aspect ratio greater than 1. Non-limiting examples of anisotropicbiomolecules include bacteriophages, amyloid fibers, and capsids.

“Turnover number” is a measure of the number of reactant molecules acatalyst can convert to product molecules per unit time.

“Active” or “catalytically active” refers to a catalyst which hassubstantial activity in the reaction of interest. For example, in someembodiments a catalyst which is OCM active (i.e., has activity in theOCM reaction) has a C2 selectivity of 5% or more and/or a methaneconversion of 5% or more when the catalyst is employed as a heterogenouscatalyst in the oxidative coupling of methane at a temperature of 750°C. or less.

“Inactive” or “catalytically inactive” refers to a catalyst which doesnot have substantial activity in the reaction of interest. For example,in some embodiments a catalyst which is OCM inactive has a C2selectivity of less than 5% and/or a methane conversion of less than 5%when the catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a temperature of 750° C. or less.

“Activation temperature” refers to the temperature at which a catalystbecomes catalytically active.

“OCM activity” refers to the ability of a catalyst to catalyse the OCMreaction.

A catalyst having “high OCM activity” refers to a catalyst having a C2selectivity of 50% or more and/or a methane conversion of 20% or morewhen the catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a specific temperature, for example750° C. or less.

A catalyst having “moderate OCM activity” refers to a catalyst having aC2 selectivity of about 20-50% and/or a methane conversion of about10-20% or more when the catalyst is employed as a heterogenous catalystin the oxidative coupling of methane at a temperature of 750° C. orless.

A catalyst having “low OCM activity” refers to a catalyst having a C2selectivity of about 5-20% and/or a methane conversion of about 5-10% ormore when the catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a temperature of 750° C. or less.

“Dopant” or “doping agent” is an impurity added to or incorporatedwithin a catalyst to optimize catalytic performance (e.g. increase ordecrease catalytic activity). As compared to the undoped catalyst, adoped catalyst may increase or decrease the selectivity, conversion,and/or yield of a reaction catalyzed by the catalyst.

“Atomic percent” (at % or at/at) or “atomic ratio” when used in thecontext of nanowire dopants refers to the ratio of the total number ofdopant atoms to the total number of metal atoms in the nanowire. Forexample, the atomic percent of dopant in a lithium doped Mg₆MnO₈nanowire is determined by calculating the total number of lithium atomsand dividing by the sum of the total number of magnesium and manganeseatoms and multiplying by 100 (i.e., atomic percent of dopant=[Liatoms/(Mg atoms+Mn atoms)]×100).

“Weight percent” (wt/wt)” when used in the context of nanowire dopantsrefers to the ratio of the total weight of dopant to the total combinedweight of the dopant and the nanowire. For example, the weight percentof dopant in a lithium doped Mg₆MnO₈ nanowire is determined bycalculating the total weight of lithium and dividing by the sum of thetotal combined weight of lithium and Mg₆MnO₈ and multiplying by 100(i.e., weight percent of dopant=[Li weight/(Li weight+Mg₆MnO₈weight)]×100).

An “extrudate” refers to a material (e.g., catalytic material) preparedby forcing a semisolid material comprising a catalyst through a die oropening of appropriate shape. Extrudates can be prepared in a variety ofshapes and structures by common means known in the art.

A “pellet” or “pressed pellet” refers to a material (e.g., catalyticmaterial) prepared by applying pressure to (i.e., compressing) amaterial comprising a catalyst into a desired shape. Pellets havingvarious dimensions and shapes can be prepared according to commontechniques in the art.

“Monolith” or “monolith support” is generally a structure formed from asingle structural unit preferably having passages disposed through it ineither an irregular or regular pattern with porous or non-porous wallsseparating adjacent passages. Examples of such monolithic supportsinclude, e.g., ceramic or metal foam-like or porous structures. Thesingle structural unit may be used in place of or in addition toconventional particulate or granular catalysts (e.g., pellets orextrudates). Examples of such irregular patterned monolith substratesinclude filters used for molten metals. Monoliths generally have aporous fraction ranging from about 60% to 90% and a flow resistancesubstantially less than the flow resistance of a packed bed of similarvolume (e.g., about 10% tp 30% of the flow resistance of a packed bed ofsimilar volume). Examples of regular patterned substrates includemonolith honeycomb supports used for purifying exhausts from motorvehicles and used in various chemical processes and ceramic foamstructures having irregular passages. Many types of monolith supportstructures made from conventional refractory or ceramic materials suchas alumina, zirconia, yttria, silicon carbide, and mixtures thereof, arewell known and commercially available from, among others, Corning, lac.;Vesuvius Hi-Tech Ceramics, Inc.; and Porvair Advanced Materials, Inc.and SiCAT (Sicatalyst.com). Monoliths include foams, honeycombs, foils,mesh, guaze and the like.

“Group 1” elements include lithium (Li), sodium (Na), potassium (K),rubidium (Rb), cesium (Cs), and francium (Fr).

“Group 2” elements include beryllium (Be), magnesium (Mg), calcium (Ca),strontium (Sr), barium (Ba), and radium (Ra).

“Group 3” elements include scandium (Sc) and yttrium (Y).

“Group 4” elements include titanium (Ti), zirconium (Zr), halfnium (Hf),and rutherfordium (Rf).

“Group 5” elements include vanadium (V), niobium (Nb), tantalum (Ta),and dubnium (Db).

“Group 6” elements include chromium (Cr), molybdenum (Mo), tungsten (W),and seaborgium (Sg).

“Group 7” elements include manganese (Mn), technetium (Tc), rhenium(Re), and bohrium (Bh).

“Group 8” elements include iron (Fe), ruthenium (Ru), osmium (Os), andhassium (Hs).

“Group 9” elements include cobalt (Co), rhodium (Rh), iridium (Ir), andmeitnerium (Mt).

“Group 10” elements include nickel (Ni), palladium (Pd), platinum (Pt)and darmistadium (Ds).

“Group 11” elements include copper (Cu), silver (Ag), gold (Au), androentgenium (Rg).

“Group 12” elements include zinc (Zn), cadmium (Cd), mercury (Hg), andcopernicium (Cn).

“Lanthanides” include lanthanum (La), cerium (Ce), praseodymium (Pr),neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu),gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium(Er), thulium (Tm), yitterbium (Yb), and lutetium (Lu).

“Actinides” include actinium (Ac), thorium (Th), protactinium (Pa),uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium(Cm), berklelium (Bk), californium (Cf), einsteinium (Es), fermium (Fm),mendelevium (Md), nobelium (No), and lawrencium (Lr).

“Rare earth” elements include Group 3, lanthanides and actinides.

“Metal element” or “metal” is any element, except hydrogen, selectedfrom Groups 1 through 12, lanthanides, actinides, aluminum (Al), gallium(Ga), indium (In), tin (Sn), thallium (Tl), lead (Pb), and bismuth (Bi).Metal elements include metal elements in their elemental form as well asmetal elements in an oxidized or reduced state, for example, when ametal element is combined with other elements in the form of compoundscomprising metal elements. For example, metal elements can be in theform of hydrates, salts, oxides, as well as various polymorphs thereof,and the like.

“Semi-metal element” refers to an element selected from boron (B),silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium(Te), and polonium (Po).

“Non-metal element” refers to an element selected from carbon (C),nitrogen (N), oxygen (O), fluorine (F), phosphorus (P), sulfur (S),chlorine (Cl), selenium (Se), bromine (Br), iodine (I), and astatine(At).

“C2” refers to a hydrocarbon (i.e., compound consisting of carbon andhydrogen atoms) having only two carbon atoms, for example ethane andethylene. Similarily, “C3” refers to a hydrocarbon having only 3 carbonatoms, for example propane and propylene.

“Conversion” means the mole fraction (i.e., percent) of a reactantconverted to a product or products.

“Selectivity” refers to the percent of converted reactant that went to aspecified product, e.g., C2 selectivity is the % of converted methanethat formed ethane and ethylene, C3 selectivity is the % of convertedmethane that formed propane and propylene, CO selectivity is the % ofconverted methane that formed CO.

“Yield” is a measure of (e.g. percent) of product obtained relative tothe theoretical maximum product obtainable. Yield is calculated bydividing the amount of the obtained product in moles by the theoreticalyield in moles. Percent yield is calculated by multiplying this value by100. C2 yield is defined as the sum of the ethane and ethylene molarflow at the reactor outlet multiplied by two and divided by the inletmethane molar flow. C3 yield is defined as the sum of propane andpropylene molar flow at the reactor outlet multiplied by three anddivided by the inlet methane molar flow. C2+ yield is the sum of the C2yield and C3 yield. Yield is also calculable by multiplying the methaneconversion by the relevant selectivity, e.g. C2 yield is equal to themethane conversion times the C2 selectivity.

“Bulk catalyst” or “bulk material” means a catalyst prepared bytraditional techniques, for example by milling or grinding largecatalyst particles to obtain smaller/higher surface area catalystparticles. Bulk materials are prepared with minimal control over thesize and/or morphology of the material.

“Alkane” means a straight chain or branched, noncyclic or cyclic,saturated aliphatic hydrocarbon. Alkanes include linear, branched andcyclic structures. Representative straight chain alkanes includemethane, ethane, n-propane, n-butane, n-pentane, n-hexane, and the like;while branched alkanes include isopropane, sec-butane, isobutanel,tert-butane, isopentane, and the like. Representative cyclic alkanesinclude cyclopropane, cyclobutane, cyclopentane, cyclohexane, and thelike. “Alkene” means a straight chain or branched, noncyclic or cyclic,unsaturated aliphatic hydrocarbon having at least one carbon-carbondouble bond. Alkenes include linear, branched and cyclic structures.Representative straight chain and branched alkenes include ethylene,propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, and thelike. Cyclic alkenes include cyclohexene and cyclopentene and the like.

“Alkyne” means a straight chain or branched, noncyclic or cyclic,unsaturated aliphatic hydrocarbon having at least one carbon-carbontriple bond. Alkynes include linear, branched and cyclic structures.Representative straight chain and branched alkynes include acetylene,propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 3-methyl-1-butyne,and the like. Representative cyclic alkynes include cycloheptyne and thelike.

“Alkyl,” “alkenyl” and “alkynyl” refers to an alkane, alkene or alkyneradical, respectively.

“Aromatic” means a carbocyclic moiety having a cyclic system ofconjugated p orbitals forming a delocalized conjugated π system and anumber of π electrons equal to 4n+2 with n=0, 1, 2, 3, etc.Representative examples of aromatics include benzene and naphthalene andtoluene. “Aryl” refers to an aromatic radical. Exemplary aryl groupsinclude, but are not limited to, phenyl, napthyl and the like.

“Carbon-containing compounds” are compounds that comprise carbon.Non-limiting examples of carbon-containing compounds includehydrocarbons, CO and CO₂.Nanowires

1. Structure/Physical Characteristics

As noted above, disclosed herein are nanowires useful as catalysts.Catalytic nanowires, and methods for preparing the same, are alsodescribed in PCT Pub. No.

2011/149996 and U.S. application. Ser. No. 13/689,514, filed on Nov. 29,2012 and entitled

“Polymer Templated Nanowire Catalysts,” the full disclosures of whichare incorporated herein by reference in their entireties. FIG. 3A is aTEM image of a polycrystalline nanowire 200 having two distal ends 210and 220. As shown, an actual length 230 essentially traces along thebackbone of the nanowire 200, whereas an effective length 234 is theshortest distance between the two distal ends. The ratio of theeffective length to the actual length is an indicator of the degrees oftwists, bends and/or kinks in the general morphology of the nanowire.FIG. 3B is a schematic representation of the nanowire 200 of FIG. 3A.Typically, the nanowire is not uniform in its thickness or diameter. Atany given location along the nanowire backbone, a diameter (240 a, 240b, 240 c, 240 d) is the longest dimension of a cross section of thenanowire, i.e., is perpendicular to the axis of the nanowire backbone).

Compared to nanowire 200 of FIG. 3A, nanowire 250 of FIG. 4A has adifferent morphology and does not exhibit as many twists, bends andkinks, which suggests a different underlying crystal structure anddifferent number of defects and/or stacking faults. As shown, fornanowire 250, the ratio of the effective length 270 and the actuallength 260 is greater than the ratio of the effective length 234 and theactual length 240 of nanowire 200 of FIG. 3A. FIG. 4B is a schematicrepresentation of the nanowire 250, which shows non-uniform diameters(280 a, 280 b, 280 c and 280 d).

As noted above, in some embodiments nanowires having a “bent” morphology(i.e. “bent nanowires”) are provided. A “bent” morphology means that thebent nanowires comprise various twists, bends and/or kinks in theirgeneral morphology as illustrated generally in FIGS. 3A and 3B anddiscussed above. Bent nanowires have a ratio of effective length toactual length of less than one. Accordingly, in some embodiments thepresent disclosure provides nanowires having a ratio of effective lengthto actual length of less than one. In other embodiments, the nanowireshave a ratio of effective length to actual length of between 0.99 and0.01, between 0.9 and 0.1, between 0.8 and 0.2, between 0.7 and 0.3, orbetween 0.6 and 0.4. In other embodiments, the ratio of effective lengthto actual length is less than 0.99, less than 0.9, less than 0.8, lessthan 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3,less than 0.2 or less than 0.1. In other embodiments, the ratio ofeffective length to actual length is less than 1.0 and more than 0.9,less than 1.0 and more than 0.8, less than 1.0 and more than 0.7, lessthan 1.0 and more than 0.6, less than 1.0 and more than 0.5, less than1.0 and more than 0.4, less than 1.0 and more than 0.3, less than 1.0and more than 0.2, or less than 1.0 and more than 0.1.

The ratio of effective length to actual length of a nanowire having abent morphology may vary depending on the angle of observation. Forexample, one-skilled in the art will recognize that the same nanowire,when observed from different perspectives, can have a differenteffective length as determined by TEM. In addition, not all nanowireshaving a bent morphology will have the same ratio of effective length toactual length. Accordingly, in a population (i.e. plurality) ofnanowires having a bent morphology, a range of ratios of effectivelength to actual length is expected. Although the ratio of effectivelength to actual length may vary from nanowire to nanowire, nanowireshaving a bent morphology will always have a ratio of effective length toactual length of less than one from any angle of observation.

In various embodiments, a substantially straight nanowire is provided. Asubstantially straight nanowire has a ratio of effective length toactual length equal to one. Accordingly, in some embodiments, thenanowires of the present disclosure have a ratio of effective length toactual length equal to one.

The actual lengths of the nanowires disclosed herein may vary. Forexample in some embodiments, the nanowires have an actual length ofbetween 100 nm and 100 μm. In other embodiments, the nanowires have anactual length of between 100 nm and 10 μm. In other embodiments, thenanowires have an actual length of between 200 nm and 10 μm. In otherembodiments, the nanowires have an actual length of between 500 nm and 5μm. In other embodiments, the actual length is greater than 5 μm. Inother embodiments, the nanowires have an actual length of between 800 nmand 1000 nm. In other further embodiments, the nanowires have an actuallength of 900 nm. As noted below, the actual length of the nanowires maybe determined by TEM, for example, in bright field mode at 5 keV.

The diameter of the nanowires may be different at different points alongthe nanowire backbone. However, the nanowires comprise a mode diameter(i.e. the most frequently occurring diameter). As used herein, thediameter of a nanowire refers to the mode diameter. In some embodiments,the nanowires have a diameter of between 1 nm and 10 μm, between 1 nmand 1 μm, between 1 nm and 500 nm, between 1 nm and 100 nm, between 7 nmand 100 nm, between 7 nm and 50 nm, between 7 nm and 25 nm, or between 7nm and 15 nm. On other embodiments, the diameter is greater than 500 nm.As noted below, the diameter of the nanowires may be determined by TEM,for example, in bright field mode at 5 keV.

Various embodiments of the present disclosure provide nanowires havingdifferent aspect ratios. In some embodiments, the nanowires have anaspect ratio of greater than 10:1. In other embodiments, the nanowireshave an aspect ratio greater than 20:1. In other embodiments, thenanowires have an aspect ratio greater than 50:1. In other embodiments,the nanowires have an aspect ratio greater than 100:1.

In some embodiments, the nanowires comprise a solid core while in otherembodiments, the nanowires comprise a hollow core.

The morphology of a nanowire (including length, diameter, and otherparameters) can be determined by transmission electron microscopy (TEM).Transmission electron microscopy (TEM) is a technique whereby a beam ofelectrons is transmitted through an ultra thin specimen, interactingwith the specimen as it passes through. An image is formed from theinteraction of the electrons transmitted through the specimen. The imageis magnified and focused onto an imaging device, such as a fluorescentscreen, on a layer of photographic film or detected by a sensor such asa CCD camera. TEM techniques are well known to those of skill in theart.

A TEM image of nanowires may be taken, for example, in bright field modeat 5 keV (e.g., as shown in FIGS. 3A and 4A).

The nanowires of the present disclosure can be further characterized bypowder x-ray diffraction (XRD). XRD is a technique capable of revealinginformation about the crystallographic structure, chemical composition,and physical properties of materials, including nanowires. XRD is basedon observing the diffracted intensity of an X-ray beam hitting a sampleas a function of incident and diffraction angle, polarization, andwavelength or energy.

Crystal structure, composition, and phase, including the crystal domainsize of the nanowires, can be determined by XRD. In some embodiments,the nanowires comprise a single crystal domain (i.e. singlecrystalline). In other embodiments, the nanowires comprise multiplecrystal domains (i.e. polycrystalline). In some other embodiments, theaverage crystal domain of the nanowires is less than 100 nm, less than50 nm, less than 30 nm, less than 20 nm, less than 10 nm, less than 5nm, or less than 2 nm.

Typically, a catalytic material described herein comprises a pluralityof nanowires. In certain embodiments, the plurality of nanowires form amesh of randomly distributed and, to various degrees, interconnectednanowires. FIG. 5A is a TEM image of a nanowire mesh 300 comprising aplurality of nanowires 310 and a plurality of pores 320. FIG. 5B is aschematic representation of the nanowire mesh 300 of FIG. 5A.

The total surface area per gram of a nanowire or plurality of nanowiresmay have an effect on the catalytic performance. Pore size distributionmay affect the nanowires catalytic performance as well. Surface area andpore size distribution of the nanowires or plurality of nanowires can bedetermined by BET (Brunauer, Emmett, Teller) measurements. BETtechniques utilize nitrogen adsorption at various temperatures andpartial pressures to determine the surface area and pore sizes ofcatalysts. BET techniques for determining surface area and pore sizedistribution are well known in the art.

In some embodiments the nanowires have a surface area of between 0.0001and 3000 m²/g, between 0.0001 and 2000 m²/g, between 0.0001 and 1000m²/g, between 0.0001 and 500 m²/g, between 0.0001 and 100 m²/g, between0.0001 and 50 m²/g, between 0.0001 and 20 m²/g, between 0.0001 and 10m²/g or between 0.0001 and 5 m²/g.

In some embodiments the nanowires have a surface area of between 0.001and 3000 m²/g, between 0.001 and 2000 m²/g, between 0.001 and 1000 m²/g,between 0.001 and 500 m²/g, between 0.001 and 100 m²/g, between 0.001and 50 m²/g, between 0.001 and 20 m²/g, between 0.001 and 10 m²/g orbetween 0.001 and 5 m²/g.

In some other embodiments the nanowires have a surface area of between2000 and 3000 m²/g, between 1000 and 2000 m²/g, between 500 and 1000m²/g, between 100 and 500 m²/g, between 10 and 100 m²/g, between 5 and50 m²/g, between 2 and 20 m²/g or between 0.0001 and 10 m²/g.

In other embodiments, the nanowires have a surface area of greater than2000 m²/g, greater than 1000 m²/g, greater than 500 m²/g, greater than100 m²/g, greater than 50 m²/g, greater than 20 m²/g, greater than 10m²/g, greater than 5 m²/g, greater than 1 m²/g, greater than 0.0001m²/g.

2. Chemical Composition

The catalytic nanowires may have any number of compositions andmorphologies. In some embodiments, the nanowires are inorganic. In otherembodiments, the nanowires are polycrystalline. In some otherembodiments, the nanowires are inorganic and polycrystalline. In yetother embodiments, the nanowires are single-crystalline, or in otherembodiments the nanowires are inorganic and single-crystalline. In stillother embodiments of any of the foregoing, the nanowires may have aratio of effective length to actual length of less than one and anaspect ratio of greater than ten as measured by TEM in bright field modeat 5 keV. In still other embodiments of any of the forgoing, thenanowires may comprise one or more elements from any of Groups 1 through7, lanthanides, actinides or combinations thereof.

In one embodiment, the disclosure provides a catalyst comprising aninorganic catalytic polycrystalline nanowire, the nanowire having aratio of effective length to actual length of less than one and anaspect ratio of greater than ten as measured by TEM in bright field modeat 5 keV, wherein the nanowire comprises one or more elements from anyof Groups 1 through 7, lanthanides, actinides or combinations thereof.

In some embodiments, the nanowires comprise one or more metal elementsfrom any of Groups 1-7, lanthanides, actinides or combinations thereof,for example, the nanowires may be mono-metallic, bi-metallic,tri-metallic, etc (i.e. contain one, two, three, etc. metal elements).In some embodiments, the metal elements are present in the nanowires inelemental form while in other embodiments the metal elements are presentin the nanowires in oxidized form. In other embodiments the metalelements are present in the nanowires in the form of a compoundcomprising a metal element. The metal element or compound comprising themetal element may be in the form of oxides, hydroxides, oxyhydroxides,salts, hydrated oxides, carbonates, oxy-carbonates, sulfates,phosphates, acetates, oxalates and the like. The metal element orcompound comprising the metal element may also be in the form of any ofa number of different polymorphs or crystal structures.

In certain examples, metal oxides may be hygroscopic and may changeforms once exposed to air, may absorb carbon dioxide, may be subjectedto incomplete calcination or any combination thereof. Accordingly,although the nanowires are often referred to as metal oxides, in certainembodiments the nanowires also comprise hydrated oxides, oxyhydroxides,hydroxides, oxycarbonates (or oxide carbonates), carbonates orcombinations thereof.

In other embodiments, the nanowires comprise one or more metal elementsfrom Group 1. In other embodiments, the nanowires comprise one or moremetal elements from Group 2. In other embodiments, the nanowirescomprise one or more metal elements from Group 3. In other embodiments,the nanowires comprise one or more metal elements from Group 4. In otherembodiments, the nanowires comprise one or more metal elements fromGroup 5. In other embodiments, the nanowires comprise one or more metalelements from Group 6. In other embodiments, the nanowires comprise oneor more metal elements from Group 7. In other embodiments, the nanowirescomprise one or more metal elements from the lanthanides. In otherembodiments, the nanowires comprise one or more metal elements from theactinides.

In one embodiment, the nanowires comprise one or more metal elementsfrom any of Groups 1-7, lanthanides, actinides or combinations thereofin the form of an oxide. In another embodiment, the nanowires compriseone or more metal elements from Group 1 in the form of an oxide. Inanother embodiment, the nanowires comprise one or more metal elementsfrom Group 2 in the form of an oxide. In another embodiment, thenanowires comprise one or more metal elements from Group 3 in the formof an oxide. In another embodiment, the nanowires comprise one or moremetal elements from Group 4 in the form of an oxide. In anotherembodiment, the nanowires comprise one or more metal elements from Group5 in the form of an oxide. In another embodiment, the nanowires compriseone or more metal elements from Group 6 in the form of an oxide. Inanother embodiment, the nanowires comprise one or more metal elementsfrom Group 7 in the form of an oxide. In another embodiment, thenanowires comprise one or more metal elements from the lanthanides inthe form of an oxide. In another embodiment, the nanowires comprise oneor more metal elements from the actinides in the form of an oxide.

In other embodiments, the nanowires comprise oxides, hydroxides,sulfates, carbonates, oxide carbonates, acetates, oxalates, phosphates(including hydrogenphosphates and dihydrogenphosphates), oxyhalides,hydroxihalides, oxyhydroxides, oxysulfates or combinations thereof ofone or more metal elements from any of Groups 1-7, lanthanides,actinides or combinations thereof. In some other embodiments, thenanowires comprise oxides, hydroxides, sulfates, carbonates, oxidecarbonates, oxalates or combinations thereof of one or more metalelements from any of Groups 1-7, lanthanides, actinides or combinationsthereof. In other embodiments, the nanowires comprise oxides, and inother embodiments, the nanowires comprise hydroxides. In otherembodiments, the nanowires comprise carbonates, and in otherembodiments, the nanowires comprise oxy-carbonates. In otherembodiments, the nanowires comprise Li₂CO₃, LiOH, Li₂O, Li₂C₂O₄, Li₂SO₄,Na₂CO₃, NaOH, Na₂O, Na₂C₂O₄, Na₂SO₄, K₂CO₃, KOH, K₂O, K₂C₂O₄, K₂SO₄,Cs₂CO₃, CsOH, Cs₂O, CsC₂O₄, CsSO₄, Be(OH)₂, BeCO₃, BeO, BeC₂O₄. BeSO₄,Mg(OH)₂, MgCO₃, MgO, MgC₂O₄. MgSO₄, Ca(OH)₂, CaO, CaCO₃, CaC₂O₄, CaSO₄,Y₂O₃, Y₃(CO₃)₂, Y(OH)₃, Y₂(C₂O₄)₃, Y₂(SO4)₃, Zr(OH)₄, ZrO(OH)₂, ZrO₂,Zr(C₂O₄)₂, Zr(SO₄)₂, Ti(OH)₄, TiO(OH)₂, TiO2, Ti(C₂O₄)₂, Ti(SO₄)₂, BaO,Ba(OH)₂, BaCO₃, BaC₂O₄, BaSO₄, La(OH)₃, La₂O₃, La₂(C₂O₄)₃, La₂(SO₄)₃,La₂(CO₃)₃, Ce(OH)₄, CeO₂, Ce₂O₃, Ce(C₂O₄)₂, Ce(SO₄)₂, Ce(CO₃)₂, ThO₂,Th(OH)₄, Th(C₂O₄)₂, Th(SO₄)₂, Th(CO₃)₂, Sr(OH)₂, SrCO₃, SrO, SrC₂O₄,SrSO₄, Sm₂O₃, Sm(OH)₃, Sm₂(CO₃)₃, Sm₂(C₂O₃)₃, Sm₂(SO₄)₃, LiCa₂Bi₃O₄Cl₆,NaMnO₄, Na₂WO₄, NaMn/WO₄, CoWO₄, CuWO₄, K/SrCCO₃, K/Na/SrCoO₃,Na/SrCoO₃, Li/SrCoO₃, SrCoO₃, Mg₆MnO₈, LiMn₂O₄, Li/Mg₆MnO₈,Na₁₀Mn/W₅O₁₇, Mg₃Mn₃B₂O₁₀, Mg₃(BO₃)₂, molybdenum oxides, molybdenumhydroxides, molybdenum oxalates, molybdenum sulfates, Mn₂O₃, Mn₃O₄,manganese oxides, manganese hydroxides, manganese oxalates, manganesesulfates, manganese tungstates, manganese carbonates, vanadium oxides,vanadium hydroxides, vanadium oxalates, vanadium sulfates, tungstenoxides, tungsten hydroxides, tungsten oxalates, tungsten sulfates,neodymium oxides, neodymium hydroxides, neodymium carbonates, neodymiumoxalates, neodymium sulfates, europium oxides, europium hydroxides,europium carbonates, europium oxalates, europium sulfates, praseodymiumoxides, praseodymium hydroxides, praseodymium carbonates, praseodymiumoxalates, praseodymium sulfates, rhenium oxides, rhenium hydroxides,rhenium oxalates, rhenium sulfates, chromium oxides, chromiumhydroxides, chromium oxalates, chromium sulfates, potassium molybdenumoxides/silicon oxide or combinations thereof.

In other embodiments, the nanowires comprise Li₂O, Na₂O, K₂O, Cs₂O, BeOMgO, CaO, ZrO(OH)₂, ZrO2, TiO₂, TiO(OH)₂, BaO, Y₂O₃, La₂O₃, CeO₂, Ce₂O₃,ThO₂, SrO, Sm₂O₃, Nd₂O₃, Eu₂O₃, Pr₂O₃, LiCa₂Bi₃O₄Cl₆, NaMnO₄, Na₂WO₄,Na/Mn/WO₄, Na/MnWO₄, Mn/WO4, K/SrCoO₃, K/Na/SrCoO₃, K/SrCoO₃, Na/SrCoO₃,Li/SrCoO₃, SrCoO₃, Mg₆MnO₈, Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, Zr₂Mo₂O₈,molybdenum oxides, Mn₂O₃, Mn₃O₄, manganese oxides, vanadium oxides,tungsten oxides, neodymium oxides, rhenium oxides, chromium oxides, orcombinations thereof.

In still other aspects, the nanowires comprise lanthanide containingperovskites. A perovskite is any material with the same type of crystalstructure as calcium titanium oxide (CaTiO₃). Examples of perovskiteswithin the context of the present disclosure include, but are notlimited to, LaCoO₃ and La/SrCoO₃.

In other embodiments, the nanowires comprise TiO₂, Sm₂O₃, V₂O₅, MoO₃,BeO, MnO₂, MgO, La₂O₃, Nd₂O₃, Eu₂O₃, ZrO₂, SrO, Na₂WO₄, Mn/WO₄, BaO,Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, NaMnO₄, CaO orcombinations thereof. In further embodiments, the nanowires compriseMgO, La₂O₃, Nd₂O₃, Na₂WO₄, Mn/WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Na/B/Mg₆MnO₈,Li/B/Mg₆MnO₈ or combinations thereof.

In some embodiments, the nanowires comprise Mg, Ca, Sr, Ba, Y, La, W,Mn, Mo, Nd, Sm, Eu, Pr, Zr or combinations thereof, and in otherembodiments the nanowire comprises MgO, CaO, SrO, BaO, Y₂O₃, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Nd₂O₃, Sm₂O₃, Eu₂O₃, Pr₂O₃, Mg₆MnO₈, NaMnO₄,Na/Mn/W/O, Na/MnWO₄, MnWO₄ or combinations thereof.

In more specific embodiments, the nanowires comprise MgO. In otherspecific embodiments, the nanowires comprise CaO. In other embodiments,the nanowires comprise SrO. In other specific embodiments, the nanowirescomprise La₂O₃. In other specific embodiments, the nanowires compriseNa₂WO₄ and may optionally further comprise Mn/WO₄. In other specificembodiments, the nanowires comprise Mn₂O₃. In other specificembodiments, the nanowires comprise Mn₃O₄. In other specificembodiments, the nanowires comprise Mg₆MnO₈. In other specificembodiments, the nanowires comprise NaMnO₄. In other specificembodiments, the nanowires comprise Nd₂O₃. In other specificembodiments, the nanowires comprise Eu₂O₃. In other specificembodiments, the nanowires comprise Pr₂O₃. In some other embodiments,the nanowires comprise Sm₂O₃.

In certain embodiments, the nanowires comprise an oxide of a group 2element. For example, in some embodiments, the nanowires comprise anoxide of magnesium. In other embodiments, the nanowires comprise anoxide of calcium. In other embodiments, the nanowires comprise an oxideof strontium. In other embodiments, the nanowires comprise an oxide ofbarium.

In certain other embodiments, the nanowires comprise an oxide of a group3 element. For example, in some embodiments, the nanowires comprise anoxide of yttrium. In other embodiments, the nanowires comprise an oxideof scandium.

In yet other certain embodiments, the nanowires comprise an oxide of anearly lanthanide element. For example, in some embodiments, thenanowires comprise an oxide of lanthanum. In other embodiments, thenanowires comprise an oxide of cerium. In other embodiments, thenanowires comprise an oxide of praseodymium. In other embodiments, thenanowires comprise an oxide of neodymium. In other embodiments, thenanowires comprise an oxide of promethium. In other embodiments, thenanowires comprise an oxide of samarium. In other embodiments, thenanowires comprise an oxide of europium. In other embodiments, thenanowires comprise an oxide of gadolinium.

In certain other embodiments, the nanowires comprise a lanthanide in theform of an oxy-carbonate. For example, the nanowires may compriseLn₂O₂(CO₃), where Ln represents a lanthanide. Examples in this regardinclude: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Luoxy-carbonates. In other embodiments, the nanowires comprise anoxy-carbonate of one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof. Accordingly in oneembodiment the nanowires comprise Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr,Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc or Reoxy-carbonate. In other embodiments, the nanowires comprise Ac, Th, U orPa oxide carbonate. An oxy-carbonate may be represented by the followingformula: M_(x)O_(y)(CO₃)_(z), wherein M is a metal element from any ofGroups 1 through 7, lanthanides or actinides and x, y and z are integerssuch that the overall charge of the metal oxy-carbonate is neutral.

In certain other embodiments, the nanowires comprise a carbonate of agroup 2 element. For example, the nanowires may comprise MgCO₃, CaCO₃,SrCO₃, BaCO₃ or combination thereof. In other embodiments, the nanowirescomprise a carbonate of one or more elements from any of the Group 1through 7, lanthanides and actinides or combination thereof. Accordinglyin one embodiment the nanowires comprise a Li, Na, K, Rb, Cs, Fr, Be,Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Paor U carbonate.

In other embodiments, the nanowires comprise TiO₂, Sm₂O₃, V₂O₅, MoO₃,BeO, MnO₂, MgO, La₂O₃, ZrO₂, SrO, Na₂WO₄, BaCO₃, Mn₂O₃, Mn₃O₄, Mg₆MnO₈,Na/B/Mg₆MnO₈, Li/B/Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄, CaO or combinationsthereof and further comprise one or more dopants comprised of metalelements, semi-metal elements, non-metal elements or combinationsthereof. In some further embodiments, the nanowires comprise MgO, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄ or combinations thereof,and the nanowires further comprise Li, Sr, Zr, Ba, Mn or Mn/WO₄.

In some embodiments, the nanowires or a catalytic material comprising aplurality of the nanowires comprise a combination of one or more ofmetal elements from any of Groups 1-7, lanthanides or actinides and oneor more of metal elements, semi-metal elements or non-metal elements.For example in one embodiment, the nanowires comprise the combinationsof Li/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O, Zr/V/P/O, Mo/V/Sb/O,V₂O₅/Al₂O₃, Mo/V/O, V/Ce/O, V/Ti/P/O, V₂O₅/TiO₂, V/P/O/TiO₂,V/P/O/Al₂O₃, V/Mg/O, V₂O₅/ZrO₂, Mo/V/Te/O, V/Mo/O/Al₂O₃, Ni/V/Sb/O,Co/V/Sb/O, Sn/V/Sb/O, Bi/V/Sb/O, Mo/V/Te/Nb/O, Mo/V/Nb/O, V₂O₅/MgO/SiO₂,V/Co, MoO₃/Al₂O₃, Ni/Nb/O, NiO/Al₂O₃, Ga/Cr/Zr/P/O, MoO₃/Cl/SiO₂/TiO₂,Co/Cr/Sn/W/O, Cr/Mo/O, MoO₃/Cl/SiO₂/TiO₂, Co/Ca, NiO/MgO, MoO₃/Al₂O₃,Nb/P/Mo/O, Mo/V/Te/Sb//Nb/O, La/Na/Al/O, Ni/Ta/Nb/O, Mo/Mn/V/W/O,Li/Dy/Mg/O, Sr/La/Nd/O, Co/Cr/Sn/W/O, MoO₃/SiO₂/TiO₂, Sm/Na/P/O,Sm/Sr/O, Sr/La/Nd/O, Co/P/O/TiO₂, La/Sr/Fe/Cl/O, La/Sr/Cu/Cl/O,Y/Ba/Cu/O, Na/Ca/O, V₂O₅/ZrO₂, V/Mg/O, Mn/V/Cr/W/O/Al₂O₃, V₂O₅/K/SiO₂,V₂O₅/Ca/TiO₂, V₂O₅/K/TiO₂, V/Mg/Al/O, V/Zr/O, V/Nb/O, V₂O₅/Ga₂O₃,V/Mg/Al/O, V/Nb/O, V/Sb/O, V/Mn/O, V/Nb/O/Sb₂O₄, V/Sb/O/TiO₂, V₂O₅/Ca,V₂O₅/K/Al₂O₃, V₂O₅/TiO₂, V₂O₅/MgO/TiO₂, V₂O₅/ZrO₂, V/Al/F/O,V/Nb/O/TiO₂, Ni/V/O, V₂O₅/SmVO₄, V/W/O, V₂O₅/Zn/Al₂O₃, V₂O₅/CeO₂,V/Sm/O, V₂O₅/TiO₂/SiO₂, Mo/Li/O/Al₂O₃, Mg/Dy/Li/Cl/O, Mg/Dy/Li/Cl/O,Ce/Ni/O, Ni/Mo/O/V, Ni/Mo/O/V/N, Ni/Mo/O Sb/O/N, MoO₃/Cl/SiO₂/TiO₂,Co/Mo/O, Ni/Ti/O, Ni/Zr/O, Cr/O, MoO₃/Al₂O₃, Mn/P/O, MoO₃/K/ZrO₂,Na/W/O, Mn/Na/W/O, Mn/Na//W/O/SiO₂, Na/W/O/SiO₂, Mn/Mo/O, Nb₂O₅/TiO₂,Co/W/O, Ni/Mo/O, Ga/Mo/O, Mg/Mo/V/O, Cr₂O₃/Al₂O₃, Cr/Mo/Cs/O/Al₂O₃,Co/Sr/O/Ca, Ag/Mo/P/O, MoO₃/SmVO₄, Mo/Mg/Al/O, MoO₃/K/SiO₂/TiO₂,Cr/Mo/O/Al₂O₃, MoO₃/Al₂O₃, Ni/Co/Mo/O, Y/Zr/O, Y/Hf, Zr/Mo/Mn/O,Mg/Mn/O, Li/Mn/O, Mg/Mn/B/O, Mg/B/O, Na/B/Mg/Mn/O, Li/B/Mg/Mn/O,Mn/Na/P/O, Na/Mn/Mg/O, Zr/Mo/O, Mn/W/O or Mg/Mn/O.

In a specific embodiment, the nanowires comprise the combinations ofLi/Mg/O, Ba/Mg/O, Zr/La/O, Ba/La/O, Sr/La/O, Sr/Nd/O, La/O, Nd/O, Eu/O,Mg/La/O, Mg/Nd/O, Na/La/O, Na/Nd/O, Sm/O, Mn/Na/W/O, Mg/Mn/O,Na/B/Mg/Mn/O, Li/B/Mg/Mn/O, Zr/Mo/O or Na/Mn/Mg/O. For example, in someembodiments the nanowires comprise the combinations of Li/MgO, Ba/MgO,Sr/La₂O₃, Ba/La₂O₃, Mn/Na₂WO₄, Mn/Na₂WO₄/SiO₂, Mn₂O₃/Na₂WO₄,Mn₃O₄/Na₂WO₄, Li/B/Mg₆MnO₈, Na/B/Mg₆MnO₈ or NaMnO₄/MgO. In certainembodiments, the nanowire comprises Li/MgO, Ba/MgO, Sr/La₂O₃,Mg/Na/La₂O₃, Sr/Nd₂O₃, or Mn/Na₂WO₄.

In some other specific embodiments, the nanowires comprise thecombination of Li/MgO. In other specific embodiments, the nanowirescomprise the combination of Ba/MgO. In other specific embodiments, thenanowires comprise the combination of Sr/La₂O₃. In other specificembodiments, the nanowires comprise the combination of Ba/La₂O₃. Inother specific embodiments, the nanowires comprise the combination ofMn/Na₂WO₄. In other specific embodiments, the nanowires comprise thecombination of Mn/Na₂WO₄/SiO₂. In other specific embodiments, thenanowires comprise the combination of Mn₂O₃/Na₂WO₄. In other specificembodiments, the nanowires comprise the combination of Mn₃O₄/Na₂WO₄. Inother specific embodiments, the nanowires comprise the combination ofMn/WO₄/Na₂WO₄. In other specific embodiments, the nanowires comprise thecombination of Li/B/Mg₆MnO₈. In other specific embodiments, thenanowires comprise the combination of Na/B/Mg₆MnO₈. In other specificembodiments, the nanowires comprise the combination of NaMnO₄/MgO.

Polyoxyometalates (POM) are a class of metal oxides that range instructure from the molecular to the micrometer scale. The uniquephysical and chemical properties of POM clusters, and the ability totune these properties by synthetic means have attracted significantinterest from the scientific community to create “designer” materials.For example, heteropolyanions such as the well-known Keggin [XM₁₂O₄₀]⁻and Wells-Dawson [X₂M1₈O₆₂]⁻ anions (where M=W or Mo; and X=atetrahedral template such as but not limited to Si, Ge, P) andisopolyanions with metal oxide frameworks with general formulas[MO_(x)]_(n) where M=Mo, W, V, and Nb and x=4-7 are ideal candidates forOCM/ODH catalysts. Accordingly, in one embodiment the nanowires comprise[XM₁₂O₄₀]⁻ or [X₂M1₈O₆₂]⁻ anions (where M=W or Mo; and X=a tetrahedraltemplate such as but not limited to Si, Ge, P) and isopolyanions withmetal oxide frameworks with general formulas [MO_(x)]_(n) where M=Mo, W,V, and Nb and x=4-7. In some embodiments, X is P or Si.

These POM clusters have “lacunary” sites that can accommodate divalentand trivalent first row transition metals, the metal oxide clustersacting as ligands. These lacunary sites are essentially “doping” sites,allowing the dopant to be dispersed at the molecular level instead of inthe bulk which can create pockets of unevenly dispersed doped material.Because the POM clusters can be manipulated by standard synthetictechniques, POMs are highly modular and a wide library of materials canbe prepared with different compositions, cluster size, and dopantoxidation state. These parameters can be tuned to yield desired OCM/ODHcatalytic properties. Accordingly, one embodiment of the presentdisclosure is a nanowire comprising one or more POM clusters. Suchnanowires find utility as catalysts, for example, in the OCM and ODHreactions.

Silica doped sodium manganese tungstate (NaMn/WO₄/SiO₂) is a promisingOCM catalyst. The NaMn/WO₄/SiO₂ system is attractive due to its high C2selectivity and yield. Unfortunately, good catalytic activity is onlyachievable at temperatures greater than 800° C. and although the exactactive portion of the catalyst is still subject to debate, it is thoughtthat sodium plays an important role in the catalytic cycle. In addition,the NaMn/WO₄/SiO₂ catalyst surface area is relatively low <2 m²/g.Manganese tungstate (Mn/WO₄) nanorods (i.e., straight nanowires) can beused to model a NaMn/WO₄/SiO₂ based nanowire OCM catalyst. The Mn/WO₄nanorods are prepared hydro-thermally and the size can be tuned based onreaction conditions with dimensions of 25-75 nm in diameter to 200-800nm in length. The as-prepared nano-rods have higher surface areas thanthe NaMn/WO₄/SiO₂ catalyst systems. In addition, the amount of sodium,or other elements, can be precisely doped into the Mn/WO₄ nanorodmaterial to target optimal catalytic activity. Nanorod tungstate basedmaterials can be expanded to, but not limited to, CoWO₄ or CuWO₄materials, which may serve as base materials for OCM/ODH catalysis. Inaddition to straight nanowires, the above discussion applies to thedisclosed nanowires having a bent morphology as well. The nanowires ofthe disclosure may be analyzed by inductively coupled plasma massspectrometry (ICP-MS) to determine the element content of the nanowires.ICP-MS is a type of mass spectrometry that is highly sensitive andcapable of the determination of a range of metals and several non-metalsat concentrations below one part in 10¹². ICP is based on couplingtogether an inductively coupled plasma as a method of producing ions(ionization) with a mass spectrometer as a method of separating anddetecting the ions. ICP-MS methods are well known in the art.

In some embodiments, the nanowire comprises a combination of two or moremetal compounds, for example metal oxides. For example, in someembodiments, the nanowire comprises Mn₂O₃/Na₂WO₄, Mn₃O₄/Na₂WO₄MnWO₄/Na₂WO₄/Mn₂O₃, MnWO₄/Na₂WO₄/Mn₃O₄ or NaMnO₄/MgO.

Certain rare earth compositions have been found to be useful catalysts,for example as catalysts in the OCM reaction. Thus, in one embodiment,the nanowire catalysts comprise lanthanide oxides such as La₂O₃, Nd₂O₃,Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃ or Pr₂O₃. In other embodiments, thenanowires comprise mixed oxides of lanthanide metals. Such mixed oxidesare represented by Ln1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are eachindependently a lanthanide element and x is a number ranging fromgreater than 0 to less than 4. In other more specific embodiments, thelanthanide mixed oxides comprise La_(4-x)Ln1_(x)O₆, wherein Ln1 is alanthanide element and x is a number ranging from greater than 0 to lessthan 4. For example, in some embodiments the lanthanide mixed oxides aremixed oxides of lanthanum and neodymium and the nanowires compriseLa_(4-x)Nd_(x)O₆, wherein x is a number ranging from greater than 0 toless than 4 have also been found to be useful in the OCM reaction. Forexample La₃NdO₆, LaNd₃O₆, La_(1.6)Nd_(2.6)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, orcombinations thereof have been found to be useful OCM catalystcompositions.

Any of the foregoing nanowire catalysts may have any morphology (e.g.,bent, straight, etc.) and may be prepared via any method describedherein or known in the art. For example, these nanowires may be preparedfrom phage or another biological template, or the nanowires may beprepared in the absence of a template, for example by hydrothermalmethods. Also as discussed below, certain dopant combinations with theabove lanthanide nanowires have been found to be useful for enhancingthe catalytic activity of the nanowires.

In other embodiments the nanowires are in a core/shell arrangement (seebelow) and the nanowires comprise Eu on a MgO core; La on a MgO core; Ndon a MgO core; Sm on a MgO core; Y—Ce on a Na doped MgO core Na or Nadoped Ce—Y on a MgO core.

In an aspect of the invention, nanowires, and materials comprising thesame, having the empirical formula M4_(w)M5_(x)M6_(y)O_(z) are provided,wherein each M4 is independently one or more elements selected fromGroups 1 through 4, each M5 is independently one or more elementsselected from Group 7 and M6 is independently one or more elementsselected from Groups 5 through 8 and Groups 14 through 15 and w, x, yand z are integers such that the overall charge is balanced.

In some embodiments, M4 comprises one or more elements selected fromGroup 1, such as sodium (Na), while M6 includes one or more elementsselected from Group 6, such as tungsten (W) and M5 is Mn. In anotherembodiment, M4 is Na, M5 is Mn, M6 is W, the ratio of w:x is 10:1, andthe ratio of w:y is 2:1. In such a case, the overall empirical formulaof the nanowire is Na₁₀MnW₆O_(z). When Na is in the +1 oxidation state,W is in the +6 oxidation state, and Mn is in the +4 oxidation state, zmust equal 17 so as to fill the valence requirements of Na, W and Mn. Asa result, the overall empirical formula of the nanowire in thisembodiment is Na₁₀MnW₅O₁₇.

In other embodiments, the ratios of w:x can be 1:1, or 5:1, or 15:1, or25:1, or 50:1. In yet other embodiments, for any given ratio of w:x, theratios of w:y can be 1:5, or 1:2, or 1:2, or 5:1. In still otherembodiments, any nanowire of the empirical formulaM4_(w)M5_(x)M6_(y)O_(z), including the nanowire of the empirical formulaM4₁₀MnM6₅O₁₇ described above, can be supported on an oxide substrate.Oxide substrates can include silica, alumina, and titania. The reactionthat anchors nanowire materials onto oxide substrates is analogous tothe reaction that anchors bulk materials onto oxide substrates, such asthat described in U.S. Pat. No. 4,808,563, which is entirelyincorporated herein by reference. Example 18 describes the anchoring ofnanowire material Na₁₀MnW₅O₁₇ onto a silica substrate. Alternatively,non-oxide support, for example silicon carbide can be used to supportnanowires of the present invention, for example Na₁₀MnW₅O₁₇ nanowiresand others. Silicon carbide has very good high temperature stability andchemical inertness toward OCM reaction intermediates and thus isparticularily effective as a support in this reaction.

3. Catalytic Materials

As noted above, the present disclosure provides a catalytic materialcomprising a plurality of nanowires. In some embodiments, the disclosureprovides a catalytic material comprising a plurality of inorganiccatalytic polycrystalline nanowires, the plurality of nanowires having aratio of average effective length to average actual length of less thanone and an average aspect ratio of greater than ten as measured by TEMin bright field mode at 5 keV, wherein the plurality of nanowirescomprises one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof.

In certain embodiments, the catalytic material comprises a support orcarrier. The support is preferably porous and has a high surface area.In some embodiments the support is active (i.e. has catalytic activity).In other embodiments, the support is inactive (i.e. non-catalytic). Insome embodiments, the support comprises an inorganic oxide, Al₂O₃, SiO₂,TiO₂, MgO, CaO, SrO, ZrO₂, ZnO, LiAlO₂, MgAl₂O₄, MnO, MnO₂, Mn₃O₄,La₂O₃, AlPO₄, SiO₂/Al₂O₃, activated carbon, silica gel, zeolites,activated clays, activated Al₂O₃, SiC, diatomaceous earth, magnesia,aluminosilicates, calcium aluminate, support nanowires or combinationsthereof. In some embodiments the support comprises silicon, for exampleSiO₂. In other embodiments the support comprises magnesium, for exampleMgO. In other embodiments the support comprises zirconium, for exampleZrO₂. In yet other embodiments, the support comprises lanthanum, forexample La₂O₃. In yet other embodiments, the support compriseslanthanum, for example Y₂O₃. In yet other embodiments, the supportcomprises hafnium, for example HfO₂. In yet other embodiments, thesupport comprises aluminum, for example Al₂O₃. In yet other embodiments,the support comprises gallium, for example Ga₂O₃.

In still other embodiments, the support material comprises an inorganicoxide, Al₂O₃, SiO₂, TiO₂, MgO, ZrO₂, HfO2, CaO, SrO, ZnO, LiAlO₂,MgAl₂O₄, MnO, MnO₂, Mn₂O₄, Mn₃O₄, La₂O₃, activated carbon, silica gel,zeolites, activated clays, activated Al₂O₃, diatomaceous earth,magnesia, aluminosilicates, calcium aluminate, support nanowires orcombinations thereof. For example, the support material may compriseSiO₂, ZrO₂, CaO, La₂O₃ or MgO.

In still other embodiments, the support material comprises a carbonate.For example, in some embodiments the support material comprises MgCO₃,CaCO₃, SrCO₃, BaCO₃, Y₂(CO₃)₃, La₂(CO₃)₃ or combinations thereof.

In yet other embodiments, a nanowire may serve as a support for anothernanowire. For example, a nanowire may be comprised of non-catalyticmetal elements and adhered to or incorporated within the supportnanowire is a catalytic nanowire. For example, in some embodiments, thesupport nanowires are comprised of SiO₂, MgO, CaO, SrO, TiO₂, ZrO₂,Al₂O₃, ZnO MgCO₃, CaCO₃, SrCO₃ or combinations thereof. Preparation ofnanowire supported nanowire catalysts (i.e., core/shell nanowires) isdiscussed in more detail below. The optimum amount of nanowire presenton the support depends, inter alia, on the catalytic activity of thenanowire. In some embodiments, the amount of nanowire present on thesupport ranges from 1 to 100 parts by weight nanowires per 100 parts byweight of support or from 10 to 50 parts by weight nanowires per 100parts by weight of support. In other embodiments, the amount of nanowirepresent on the support ranges from 100-200 parts of nanowires per 100parts by weight of support, or 200-500 parts of nanowires per 100 partsby weight of support, or 500-1000 parts of nanowires per 100 parts byweight of support. Typically, heterogeneous catalysts are used either intheir pure form or blended with inert materials, such as silica,alumina, etc. The blending with inert materials is used in order toreduce and/or control large temperature non-uniformities within thereactor bed often observed in the case of strongly exothermic (orendothermic) reactions. In the case of complex multistep reactions, suchas the reaction to convert methane into ethylene (OCM), typical blendingmaterials can selectively slow down or quench one or more of thereactions of the system and promote unwanted side reactions. Forexample, in the case of the oxidative coupling of methane, silica andalumina can quench the methyl radicals and thus prevent the formation ofethane. In certain aspects, the present disclosure provides a catalyticmaterial which solves these problems typically associated with catalystsupport material. Accordingly, in certain embodiments the catalyticactivity of the catalytic material can be tuned by blending two or morecatalysts and/or catalyst support materials. The blended catalyticmaterial may comprise a catalytic nanowire as described herein and abulk catalyst material and/or inert support material.

The blended catalytic materials comprise metal oxides, hydroxides,oxy-hydroxides, carbonates, oxalates of the groups 1-16, lanthanides,actinides or combinations thereof. For example, the blended catalyticmaterials may comprise a plurality of inorganic catalyticpolycrystalline nanowires, as disclosed herein, and any one or more ofstraight nanowires, nanoparticles, bulk materials and inert supportmaterials. Bulk materials are defined as any material in which noattempt to control the size and/or morphology was performed during itssynthesis. The catalytic materials may be undoped or may be doped withany of the dopants described herein.

In one embodiment, the catalyst blend comprises at least one type 1component and at least one type 2 component. Type 1 components comprisecatalysts having a high OCM activity at moderately low temperatures andtype 2 components comprise catalysts having limited or no OCM activityat these moderately low temperatures, but are OCM active at highertemperatures. For example, in some embodiments the type 1 component is acatalyst (e.g., nanowire) having high OCM activity at moderately lowtemperatures. For example, the type 1 component may comprise a C2 yieldof greater than 5% or greater than 10% at temperatures less than 800°C., less than 700° C. or less than 600° C. The type 2 component maycomprise a C2 yield less than 0.1%, less than 1% or less than 5% attemperatures less than 800° C., less than 700° C. or less than 600° C.The type 2 component may comprise a C2 yield of greater than 0.1%,greater than 1%, greater than 5% or greater than 10% at temperaturesgreater than 800° C., greater than 700° C. or greater than 600° C.Typical type 1 components include nanowires, for example polycrystallinenanowires as described herein, while typical type 2 components includebulk OCM catalysts and nanowire catalysts which only have good OCMactivity at higher temperatures, for example greater than 800° C.Examples of type 2 components may include catalysts comprising MgO. Thecatalyst blend may further comprise inert support materials as describedabove (e.g., silica, alumina, silicon carbide, etc.).

In certain embodiments, the type 2 component acts as diluent in the sameway an inert material does and thus helps reduce and/or control hotspots in the catalyst bed caused by the exothermic nature of the OCMreaction. However, because the type 2 component is an OCM catalyst,albeit not a particularly active one, it may prevent the occurrence ofundesired side reactions, e.g. methyl radical quenching. Additionally,controlling the hotspots has the beneficial effect of extending thelifetime of the catalyst.

For example, it has been found that diluting active lanthanide oxide OCMcatalysts (e.g., nanowires) with as much as a 10:1 ratio of MgO, whichby itself is not an active OCM catalyst at the temperature which thelanthanide oxide operates, is a good way to minimize “hot spots” in thereactor catalyst bed, while maintaining the selectivity and yieldperformance of the catalyst. On the other hand, doing the same dilutionwith quartz SiO₂ is not effective because it appears to quench themethyl radicals which serves to lower the selectivity to C2s.

In yet another embodiment, the type 2 components are good oxidativedehydrogenation (ODH) catalysts at the same temperature that the type 1components are good OCM catalysts. In this embodiment, theethylene/ethane ratio of the resulting gas mixture can be tuned in favorof higher ethylene. In another embodiment, the type 2 components are notonly good ODH catalysts at the same temperature the type 1 componentsare good OCM catalysts, but also have limited to moderate OCM activityat these temperatures.

In related embodiments, the catalytic performance of the catalyticmaterial is tuned by selecting specific type 1 and type 2 components ofa catalyst blend. In another embodiment, the catalytic performance istuned by adjusting the ratio of the type 1 and type 2 components in thecatalytic material. For example, the type 1 catalyst may be a catalystfor a specific step in the catalytic reaction, while the type 2 catalystmay be specific for a different step in the catalytic reaction. Forexample, the type 1 catalyst may be optimized for formation of methylradicals and the type 2 catalyst may be optimized for formation ofethane or ethylene.

In other embodiments, the catalytic material comprises at least twodifferent components (component 1, component 2, component 3, etc.). Thedifferent components may comprise different morphologies, e.g.nanowires, nanoparticles, bulk, etc. The different components in thecatalyst material can be, but not necessarily, of the same chemicalcomposition and the only difference is in the morphology and/or the sizeof the particles. This difference in morphology and particle size mayresult in a difference in reactivity at a specific temperature.Additionally, the difference in morphology and particle size of thecatalytic material components is advantageous for creating a veryintimate blending, e.g. very dense packing of the catalysts particles,which can have a beneficial effect on catalyst performance. Also, thedifference in morphology and particle size of the blend components wouldallow for control and tuning of the macro-pore distribution in thereactor bed and thus its catalytic efficiency. An additional level ofmicro-pore tuning can be attained by blending catalysts with differentchemical composition and different morphology and/or particle size. Theproximity effect would be advantageous for the reaction selectivity.

Accordingly, in one embodiment the present disclosure provides the useof a catalytic material comprising a first catalytic nanowire and a bulkcatalyst and/or a second catalytic nanowire in a catalytic reaction, forexample the catalytic reaction may be OCM or ODH. In other embodiments,the first catalytic nanowire and the bulk catalyst and/or secondcatalytic nanowire are each catalytic with respect to the same reaction,and in other examples the first catalytic nanowire and the bulk catalystand/or second catalytic nanowire have the same chemical composition.

In some specific embodiments of the foregoing, the catalytic materialcomprises a first catalytic nanowire and a second catalytic nanowire.Each nanowire can have completely different chemical compositions orthey may have the same base composition and differ only by the dopingelements. In other embodiments, each nanowire can have the same or adifferent morphology. For example, each nanowire can differ by thenanowire size (length and/or aspect ratio), by ratio of actual/effectivelength, by chemical composition or any combination thereof. Furthermore,the first and second nanowires may each be catalytic with respect to thesame reaction but may have different activity. Alternatively, eachnanowire may catalyze different reactions.

In a related embodiment, the catalytic material comprises a firstcatalytic nanowire and a bulk catalyst. The first nanowire and the bulkcatalyst can have completely different chemical compositions or they mayhave the same base composition and differ only by the doping elements.Furthermore, the first nanowire and the bulk catalyst may each becatalytic with respect to the same reaction but may have differentactivity. Alternatively, the first nanowire and the bulk catalyst maycatalyze different reactions.

In yet other embodiments of the foregoing, the catalytic nanowire has acatalytic activity in the catalytic reaction, which is greater than acatalytic activity of the bulk catalyst in the catalytic reaction at thesame temperature. In still other embodiments, the catalytic activity ofthe bulk catalyst in the catalytic reaction increases with increasingtemperature.

OCM catalysts may be prone to hotspots due to the very exothermic natureof the OCM reaction. Diluting such catalysts helps to manage thehotspots. However, the diluent needs to be carefully chosen so that theoverall performance of the catalyst is not degraded. Silicon carbide forexample can be used as a diluent with little impact on the OCMselectivity of the blended catalytic material whereas using silica as adiluent significantly reduces OCM selectivity. The good heatconductivity of SiC is also beneficial in minimizing hot spots. As notedabove, use of a catalyst diluents or support material that is itself OCMactive has significant advantages over more traditional diluents such assilica and alumina, which can quench methyl radicals and thus reduce theOCM performance of the catalyst. An OCM active diluent is not expectedto have any adverse impact on the generation and lifetime of methylradicals and thus the dilution should not have any adverse impact on thecatalyst performance. Thus embodiments of the invention include catalystcompositions comprising an OCM catalyst (e.g., any of the disclosednanowire catalysts) in combination with a diluent or support materialthat is also OCM active. Methods for use of the same in an OCM reactionare also provided.

In some embodiments, the above diluent comprises alkaline earth metalcompounds, for example alkaline metal oxides, carbonates, sulfates orphosphates. Examples of diluents useful in various embodiments include,but are not limited to, MgO, MgCO₃, MgSO₄, Mg₃(PO₄)₂, MgAl₂O₄, CaO,CaCO₃, CaSO₄, Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄,BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ and the like. Most of thesecompounds are very cheap, especially MgO, CaO, MgCO₃, CaCO₃, SrO, SrCO₃and thus very attractive for use as diluents from an economic point ofview. Additionally, the magnesium, calcium and strontium compounds areenvironmentally friendly too. Accordingly, an embodiment of theinvention provides a catalytic material comprising a catalytic nanowirein combination with a diluent selected from one or more of MgO, MgCO₃,MgSO₄, Mg₃(PO₄)₂, CaO, CaCO₃, CaSO₄, Ca₃(PO₄)₂, SrO, SrCO₃, SrSO₄,Sr₃(PO₄)₂, BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂. In some specific embodimentsthe diluents is MgO, CaO, SrO, MgCO₃, CaCO₃, SrCO₃ or combinationthereof. Methods for use of the foregoing catalytic materials in an OCMreaction are also provided. The methods comprise converting methane toethane and or ethylene in the presence of the catalytic materials.

The above diluents and supports may be employed in any number ofmethods. For example, in some embodiments a support (e.g., MgO, CaO,CaCO₃, SrCO₃) may be used in the form of a pellet or monolith (e.g.,honeycomb) structure, and the nanowire catalysts may be impregnated orsupported thereon. In other embodiments, a core/shell arrangement isprovided and the support material may form part of the core or shell.For example, a core of MgO, CaO, CaCO₃ or SrCO₃ may be coated with ashell of any of the disclosed nanowire compositions.

In some embodiments, the diluent has a morphology selected from bulk(e.g. commercial grade), nano (nanowires, nanorods, nanoparticles, etc.)or combinations thereof.

In some embodiments, the diluent has none to moderate catalytic activityat the temperature the OCM catalyst is operated. In some otherembodiments, the diluent has moderate to large catalytic activity at atemperature higher than the temperature the OCM catalyst is operated. Inyet some other embodiments, the diluent has none to moderate catalyticactivity at the temperature the OCM catalyst is operated and moderate tolarge catalytic activity at temperatures higher than the temperature theOCM catalyst is operated. Typical temperatures for operating an OCMreaction according to the present disclosure are 800° C. or lower, 750°C. or lower, 700° C. or lower, 650° C. or lower, 600° C. or lower and550° C. or lower.

For example, CaCO₃ is a relatively good OCM catalyst at T>750° C. (50%selectivity, >20% conversion) but has essentially no activity below 700°C. Experiments performed in support of the present invention showed thatdilution of Nd₂O₃ straight nanowires with CaCO₃ or SrCO₃ (bulk) showedno degradation of OCM performance and, in some cases, even betterperformance than the neat catalyst.

In some embodiments, the diluent portion in the catalyst/diluent mixtureis 0.01%, 10%, 30%, 50%, 70%, 90% or 99.99% (weight percent) or anyother value between 0.01% and 99.9%. In some embodiments, the dilutionis performed with the OCM catalyst ready to go, e.g. after calcination.In some other embodiments, the dilution is performed prior to the finalcalcination of the catalyst, i.e. the catalyst and the diluent arecalcined together. In yet some other embodiments, the dilution can bedone during the synthesis as well, so that, for example, a mixed oxideis formed.

In some embodiments, the catalyst/diluent mixture comprises more thanone catalyst and/or more than one diluent. In some other embodiments,the catalyst/diluent mixture is pelletized and sized, or made intoshaped extrudates or deposited on a monolith or foam, or is used as itis. Methods of the invention include taking advantage of the veryexothermic nature of OCM by diluting the catalyst with another catalystthat is (almost) inactive in the OCM reaction at the operatingtemperature of the first catalyst but active at higher temperature. Inthese methods, the heat generated by the hotspots of the first catalystwill provide the necessary heat for the second catalyst to becomeactive.

For ease of illustration, the above description of catalytic materialsoften refers to OCM; however, such catalytic materials find utility inother catalytic reactions including but not limited to: oxidativedehydrogenation (ODH) of alkanes to their corresponding alkenes,selective oxidation of alkanes and alkenes and alkynes, oxidation of co,dry reforming of methane, selective oxidation of aromatics,Fischer-Tropsch, combustion of hydrocarbons, etc.

4. Preparation of Catalytic Materials

The catalytic materials can be prepared according to any number ofmethods known in the art. For example, the catalytic materials can beprepared after preparation of the individual components by mixing theindividual components in their dry form, e.g. blend of powders, andoptionally, ball milling can be used to reduce particle size and/orincrease mixing. Each component can be added together or one after theother to form layered particles. Alternatively, the individualcomponents can be mixed prior to calcination, after calcination or bymixing already calcined components with uncalcined components. Thecatalytic materials may also be prepared by mixing the individualcomponents in their dry form and optionally pressing them together intoa “pill” followed by calcination to above 400° C.

In other examples, the catalytic materials are prepared by mixing theindividual components with one or more solvents into a suspension orslurry, and optional mixing and/or ball milling can be used to maximizeuniformity and reduce particle size. Examples of slurry solvents usefulin this context include, but are not limited to: water, alcohols,ethers, carboxylic acids, ketones, esters, amides, aldehydes, amines,alkanes, alkenes, alkynes, aromatics, etc. In other embodiments, theindividual components are deposited on a supporting material such assilica, alumina, magnesia, activated carbon, and the like, or by mixingthe individual components using a fluidized bed granulator. Combinationsof any of the above methods may also be used.

The catalytic materials may optionally comprise a dopant as described inmore detail below. In this respect, doping material(s) may be addedduring preparation of the individual components, after preparation ofthe individual components but before drying of the same, after thedrying step but before calcinations or after calcination. If more thanone doping material is used, each dopant can be added together or oneafter the other to form layers of dopants.

Doping material(s) may also be added as dry components and optionallyball milling can be used to increase mixing. In other embodiments,doping material(s) are added as a liquid (e.g. solution, suspension,slurry, etc.) to the dry individual catalyst components or to theblended catalytic material. The amount of liquid may optionally beadjusted for optimum wetting of the catalyst, which can result inoptimum coverage of catalyst particles by doping material. Mixing and/orball milling can also be used to maximize doping coverage and uniformdistribution. Alternatively, doping material(s) are added as a liquid(e.g. solution, suspension, slurry, etc.) to a suspension or slurry ofthe catalyst in a solvent. Mixing and/or ball milling can be used tomaximize doping coverage and uniform distribution. Incorporation ofdopants can also be achieved using any of the methods describedelsewhere herein.

As noted below, an optional calcination step usually follows an optionaldrying step at T<200 C (typically 60-120 C) in a regular oven or in avacuum oven. Calcination may be performed on the individual componentsof the catalytic material or on the blended catalytic material.Calcination is generally performed in an oven/furnace at a temperaturehigher than the minimum temperature at which at least one of thecomponents decomposes or undergoes a phase transformation and can beperformed in inert atmosphere (e.g. N₂, Ar, He, etc.), oxidizingatmosphere (air, O₂, etc.) or reducing atmosphere (H₂, H₂/N₂, H₂/Ar,etc.). The atmosphere may be a static atmosphere or a gas flow and maybe performed at ambient pressure, at p<1 atm, in vacuum or at p>1 atm.High pressure treatment (at any temperature) may also be used to inducephase transformation including amorphous to crystalline. Calcinationsmay also be performed using microwave heating.

Calcination is generally performed in any combination of stepscomprising ramp up, dwell and ramp down. For example, ramp to 500° C.,dwell at 500° C. for 5 h, ramp down to RT. Another example includes rampto 100° C., dwell at 100° C. for 2 h, ramp to 300° C., dwell at 300° C.for 4 h, ramp to 550° C., dwell at 550° C. for 4 h, ramp down to RT.Calcination conditions (pressure, atmosphere type, etc.) can be changedduring the calcination. In some embodiments, calcination is performedbefore preparation of the blended catalytic material (i.e., individualcomponents are calcined), after preparation of the blended catalyticmaterial but before doping, after doping of the individual components orblended catalytic material. Calcination may also be performed multipletimes, e.g. after catalyst preparation and after doping.

The catalytic materials may be incorporated into a reactor bed forperforming any number of catalytic reactions (e.g., OCM, ODH and thelike). Accordingly, in one embodiment the present disclosure provides acatalytic material as disclosed herein in contact with a reactor and/orin a reactor bed. For example, the reactor may be for performing an OCMreaction, may be a fixed bed reactor and may have a diameter greaterthan 1 inch. In this regard, the catalytic material may be packed neat(without diluents) or diluted with an inert material (e.g., sand,silica, alumina, etc.) The catalyst components may be packed uniformlyforming a homogeneous reactor bed.

The particle size of the individual components within a catalyticmaterial may also alter the catalytic activity, and other properties, ofthe same. Accordingly, in one embodiment, the catalyst is milled to atarget average particle size or the catalyst powder is sieved to selecta particular particle size. In some aspects, the catalyst powder may bepressed into pellets and the catalyst pellets can be optionally milledand or sieved to obtain the desired particle size distribution.

In some embodiments, the catalyst materials, alone or with bindersand/or diluents, can be configured into larger aggregate forms, such aspellets, extrudates, or other aggregations of catalyst particles. Forease of discussion, such larger forms are generally referred to hereinas “pellets”. Such pellets may optionally include a binder and/orsupport material; however, the present inventors have surprisingly foundthat the disclosed nanowires are particularly suited to used in the formof a pellet without a binder and/or support material. Accordingly, oneembodiment of the disclosure provides a catalytic material in theabsence of a binder. In this regard, the morphology of the disclosednanowires (either bent or straight, etc.) is believed to contribute tothe nanowires' ability to be pressed into pellets without the need for abinder. Catalytic materials without binders are simpler, less complexand cheaper than corresponding materials with binders and thus offercertain advantages.

In some instances, catalytic materials may be prepared using a“sacrificial binder” or support. Because of their special properties,the nanowires allow for preparation of catalytic material forms (e.g.pellets) without the use of a binder. A “sacrificial” binder can be usedin order to create unique microporosity in pellets or extrudates. Afterremoving the sacrificial binder, the structural integrity of thecatalyst is ensured by the special binding properties of the nanowiresand the resulting catalytic material has unique microporosity as aresult of removing the binder. For example, in some embodiments acatalytic nanowire may be prepared with a binder and then the binderremoved by any number of techniques (e.g., combustion, calcinations,acid erosion, etc.). This method allows for design and preparation ofcatalytic materials having unique microporosity (i.e., the microporosityis a function of size, etc. of the sacrificial binder). The ability toprepare different forms (e.g., pellets) of the nanowires without the useof binder is not only useful for preparation of catalytic materials fromthe nanowires, but also allows the nanowires to be used as supportmaterials (or both catalytic and support material). Sacrificial bindersand techniques useful in this regard include sacrificial cellulosicfibers or other organic polymers that can be easily removed bycalcination, non-sacrificial binders and techniques useful in thisregard include, colloidal oxide binders such as Ludox Silica or Nyacolcolloidal zirconia that can also be added to strengthen the formedaggregate when needed. Sacrificial binders are added to increasemacro-porosity (pores larger than 20 nm diameter) of the catalyticmaterials. Accordingly, in some embodiments the catalytic materialscomprise pores greater than 20 nm in diameter, greater than 50 nm indiameter, greater than 75 nm in diameter, greater than 100 nm indiameter or greater than 150 nm in diameter.

Catalytic materials also include any of the disclosed nanowires disposedon or adhered to a solid support. For example, the nanowires may beadhered to the surface of a monolith support. As with the binder-lessmaterials discussed above, in these embodiments the nanowires may beadhered to the surface of the monolith in the absence of a binder due totheir unique morphology and packing properties. Monoliths includehoneycomb-type structures, foams and other catalytic support structuresderivable by one skilled in the art. In one embodiment, the support is ahoneycomb matrix formed from silicon carbide, and the support furthercomprises catalytic nanowires disposed on the surface.

As the OCM reaction is very exothermic, it can be desirable to reducethe rate of conversion per unit volume of reactor in order to avoid runaway temperature rise in the catalyst bed that can result in hot spotsaffecting performance and catalyst life. One way to reduce the OCMreaction rate per unit volume of reactor is to spread the activecatalyst onto an inert support with interconnected large pores as inceramic or metallic foams (including metal alloys having reducedreactivity with hydrocarbons under OCM reaction conditions) or havingarrays of channel as in honeycomb structured ceramic or metal assembly.

In one embodiment, a catalytic material comprising a catalytic nanowireas disclosed herein supported on a structured support is provided.Examples of such structure supports include, but are not limited to,metal foams, Silicon Carbide or Alumina foams, corrugated metal foilarranged to form channel arrays, extruded ceramic honeycomb, for exampleCordierite (available from Corning or NGK ceramics, USA), SiliconCarbide or Alumina.

Active catalyst loading on the structured support ranges from 1 to 500mg per ml of support component, for example from 5 to 100 mg per ml ofstructure support. Cell densities on honeycomb structured supportmaterials may range from 100 to 900 CPSI (cell per square inch), forexample 200 to 600 CPSI. Foam densities may range from 10 to 100 PPI(pore per inch), for example 20 to 60 PPI.

In other embodiments, the exotherm of the OCM reaction may be at leastpartially controlled by blending the active catalytic material withcatalytically inert material, and pressing or extruding the mixture intoshaped pellets or extrudates. In some embodiments, these mixed particlesmay then be loaded into a pack-bed reactor. The Extrudates or pelletscomprise between 30% to 70% pore volume with 5% to 50% active catalystweight fraction. Useful inert materials in this regard include, but arenot limited to MgO, CaO, Al₂O₃, SiC and cordierite.

In addition to reducing the potential for hot spots within the catalyticreactor, another advantage of using a structured ceramic with large porevolume as a catalytic support is reduced flow resistance at the same gashourly space velocity versus a pack-bed containing the same amount ofcatalyst.

Yet another advantage of using such supports is that the structuredsupport can be used to provide features difficult to obtain in apack-bed reactor. For example the support structure can improve mixingor enabling patterning of the active catalyst depositions through thereactor volume. Such patterning can consist of depositing multiplelayers of catalytic materials on the support in addition to the OCMactive component in order to affect transport to the catalyst orcombining catalytic functions as adding O2-ODH activity, CO2-OCMactivity or CO2-ODH activity to the system in addition to O2-OCM activematerial. Another patterning strategy can be to create bypass within thestructure catalyst essentially free of active catalyst to limit theoverall conversion within a given supported catalyst volume.

Yet another advantage is reduced heat capacity of the bed of thestructured catalyst over a pack bed a similar active catalyst loadingtherefore reducing startup time.

Nanowire shaped catalysts are particularly well suited for incorporationinto pellets or extrudates or deposition onto structured supports.Nanowire aggregates forming a mesh type structure can have good adhesiononto rough surfaces.

The mesh like structure can also provide improved cohesion in compositeceramic improving the mechanical properties of pellets or extrudatescontaining the nanowire shaped catalyst particles.

Alternatively, such nanowire on support or in pellet form approaches canbe used for other reactions besides OCM, such as ODH, dry methanereforming, FT, and all other catalytic reactions.

In yet another embodiment, the catalysts are packed in bands forming alayered reactor bed. Each layer is composed by either a catalyst of aparticular type, morphology or size or a particular blend of catalysts.In one embodiment, the catalysts blend may have better sinteringproperties, i.e. lower tendency to sinter, then a material in its pureform. Better sintering resistance is expected to increase the catalyst'slifetime and improve the mechanical properties of the reactor bed.

In yet other embodiments, the disclosure provides a catalytic materialcomprising one or more different catalysts. The catalysts may be ananowire as disclosed herein and a different catalyst for example a bulkcatalysts. Mixtures of two or more nanowire catalysts are alsocontemplated. The catalytic material may comprise a catalyst, forexample a nanowire catalyst, having good OCM activity and a catalysthaving good activity in the ODH reaction. Either one or both of thesecatalysts may be nanowires as disclosed herein.

On skilled in the art will recognize that various combinations oralternatives of the above methods are possible, and such variations arealso included within the scope of the present disclosure.

5. Dopants

In further embodiments, the disclosure provides nanowires comprising adopant (i.e., doped nanowires). As noted above, dopants or doping agentsare impurities added to or incorporated within a catalyst to optimizecatalytic performance (e.g., increase or decrease catalytic activity).As compared to the undoped catalyst, a doped catalyst may increase ordecrease the selectivity, conversion, and/or yield of a catalyticreaction. In one embodiment, nanowire dopants comprise one or more metalelements, semi-metal elements, non-metal elements or combinationsthereof. Although oxygen is included in the group of nonmetal elements,in certain embodiments oxygen is not considered a dopant. For example,certain embodiments are directed to nanowires comprising two, three oreven four or more dopants, and the dopants are non-oxygen dopants. Thusin these embodiments, a metal oxide nanowire is not considered to be ametal nanowire doped with oxygen. Analagously, in the case of mixedoxides (i.e., M1_(x)M2_(y)O_(z)), both the metal elements and oxygen areconsidered a part of the base catalyst (nanowire) and are not includedin the total number of dopants.

The dopant may be present in any form and may be derived from anysuitable source of the element (e.g., chlorides, bromides, iodides,nitrates, oxynitrates, oxyhalides, acetates, formates, hydroxides,carbonates, phosphates, sulfates, alkoxides, and the like.). In someembodiments, the nanowire dopant is in elemental form. In otherembodiments, the nanowire dopant is in reduced or oxidized form. Inother embodiments, the nanowire dopant comprises an oxide, hydroxide,carbonate, nitrate, acetate, sulfate, formate, oxynitrate, halide,oxyhalide or hydroxyhalide of a metal element, semi-metal element ornon-metal element or combinations thereof.

In one embodiment, the nanowires comprise one or more metal elementsselected from Groups 1-7, lanthanides, actinides or combinations thereofin the form of an oxide and further comprise one or more dopants,wherein the one or more dopants comprise metal elements, semi-metalelements, non-metal elements or combinations thereof. In anotherembodiment, the nanowires comprise one or more metal elements selectedfrom group 1 in the form of an oxide and further comprise one or moredopants, wherein the one or more dopants comprise metal elements,semi-metal elements, non-metal elements or combinations thereof. Inanother embodiment, the nanowires comprise one or more metal elementsselected from group 2 in the form of an oxide and further comprise oneor more dopants, wherein the one or more dopants comprise metalelements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 3 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 4 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 5 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 6 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from group 7 in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from lanthanides in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof. In another embodiment, the nanowires comprise one or more metalelements selected from actinides in the form of an oxide and furthercomprise one or more dopants, wherein the one or more dopants comprisemetal elements, semi-metal elements, non-metal elements or combinationsthereof.

For example, in one embodiment, the nanowire dopant comprises Li,Li₂CO₃, LiOH, Li₂O, LiCl, LiNO₃, Na, Na₂CO₃, NaOH, Na₂O, NaCl, NaNO₃, K,K₂CO₃, KOH, K₂O, KCl, KNO₃, Rb, Rb₂CO₃, RbOH, Rb₂O, RbCl, RbNO₃, Cs,Cs₂CO₃, CsOH, Cs₂O, CsCl, CsNO₃, Mg, MgCO₃, Mg(OH)₂, MgO, MgCl₂,Mg(NO₃)₂, Ca, CaO, CaCO₃, Ca(OH)₂, CaCl₂, Ca(NO₃)₂, Sr, SrO, SrCO₃,Sr(OH)₂, SrCl₂, Sr(NO₃)₂, Ba, BaO, BaCO₃, Ba(OH)₂, BaCl₂, Ba(NO₃)₂, La,La₂O₃, La₂(CO₃)₃, La(OH)₃, LaCl₃, La(NO₃)₂, Nd, Nd₂O₃, Nd₂(CO₃)₃,Nd(OH)₃, NdCl₃, Nd(NO₃)₂, Sm, Sm₂O₃, Sm₂(CO₃)₃, Sm(OH)₃, SmCl₃,Sm(NO₃)₂, Eu, Eu₂O₃, Eu₂(CO₃)₃, Eu(OH)₃, EuCl₃, Eu(NO₃)₂, Gd, Gd₂O₃,Gd₂(CO₃)₃, Gd(OH)₃, GdCl₃, Gd(NO₃)₂, Ce, Ce(OH)₄, CeO₂, Ce₂O₃, Ce(CO₃)₂,CeCl₄, Ce(NO₃)₂, Th, ThO₂, ThCl₄, Th(OH)₄, Zr, ZrO₂, ZrCl₄, Zr(OH)₄,ZrOCl₂, Zr(CO₃)2, ZrOCO₃, ZrO(NO₃)₂, P, phosphorous oxides, phosphorouschlorides, phosphorous carbonates, Ni, nickel oxides, nickel chlorides,nickel carbonates, nickel hydroxides, Nb, niobium oxides, niobiumchlorides, niobium carbonates, niobium hydroxides, Au, gold oxides, goldchlorides, gold carbonates, gold hydroxides, Mo, molybdenum oxides,molybdenum chlorides, molybdenum carbonates, molybdenum hydroxides,tungsten chlorides, tungsten carbonates, tungsten hydroxides, Cr,chromium oxides, chromium chlorides, chromium hydroxides, Mn, manganeseoxides, manganese chlorides, manganese hydroxides, Zn, ZnO, ZnCl₂,Zn(OH)₂, B, borates, BCl₃, N, nitrogen oxides, nitrates, La, Ce, Pr, Nd,Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Y, Sc, Al, Cu, Cs, Ga,Hf, Fe, Ru, Rh, Be, Co, Sb, V, Ag, Te, Pd, Tb, Ir, Rb or combinationsthereof. In other embodiments, the nanowire dopant comprises Li, Na, K,Rb, Cs, Mg, Ca, Sr, Eu, In, Nd, Sm, Ce, Gd, Tb, Er, Tm, Yb, Y, Sc orcombinations thereof.

In other embodiments, the nanowire dopant comprises Li, Li₂O, Na, Na₂O,K, K₂O, Mg, MgO, Ca, CaO, Sr, SrO, Ba, BaO, La, La₂O₃, Ce, CeO₂, Ce₂O₃,Th, ThO₂, Zr, ZrO₂, P, phosphorous oxides, Ni, nickel oxides, Nb,niobium oxides, Au, gold oxides, Mo, molybdenum oxides, Cr, chromiumoxides, Mn, manganese oxides, Zn, ZnO, B, borates, N, nitrogen oxides orcombinations thereof. In other embodiments, the nanowire dopantcomprises Li, Na, K, Mg, Ca, Sr, Ba, La, Ce, Th, Zr, P, Ni, Nb, Au, Mo,Cr, Mn, Zn, B, N or combinations thereof. In other embodiments, thenanowire dopant comprises Li₂O, Na₂O, K₂O, MgO, CaO, SrO, BaO, La₂O₃,CeO₂, Ce₂O₃, ThO₂, ZrO₂, phosphorous oxides, nickel oxides, niobiumoxides, gold oxides, molybdenum oxides, chromium oxides, manganeseoxides, ZnO, borates, nitrogen oxides or combinations thereof. Infurther embodiments, the dopant comprises Sr or Li. In other specificembodiments, the nanowire dopant comprises La, Ce, Pr, Nd, Pm, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Y, Sc or combinations thereof. Inother specific embodiments, the nanowire dopant comprises Li, Na, K, Mg,Ca, Ba, Sr, Eu, Sm, Co or Mn.

In certain embodiments, the dopant comprises an element from group 1. Insome embodiments, the dopant comprises lithium. In some embodiments, thedopant comprises sodium. In some embodiments, the dopant comprisespotassium. In some embodiments, the dopant comprises rubidium. In someembodiments, the dopant comprises caesium.

In some embodiments the nanowires comprise a lanthanide element and aredoped with a dopant from group 1, group 2, or combinations thereof. Forexample, in some embodiments, the nanowires comprise a lanthanideelement and are doped with lithium. In other embodiments, the nanowirescomprise a lanthanide element and are doped with sodium. In otherembodiments, the nanowires comprise a lanthanide element and are dopedwith potassium. In other embodiments, the nanowires comprise alanthanide element and are doped with rubidium. In other embodiments,the nanowires comprise a lanthanide element and are doped with caesium.In other embodiments, the nanowires comprise a lanthanide element andare doped with beryllium. In other embodiments, the nanowires comprise alanthanide element and are doped with magnesium. In other embodiments,the nanowires comprise a lanthanide element and are doped with calcium.In other embodiments, the nanowires comprise a lanthanide element andare doped with strontium. In other embodiments, the nanowires comprise alanthanide element and are doped with barium.

In some embodiments the nanowires comprise a transition metal tungstate(e.g., Mn/W and the like) and are doped with a dopant from group 1,group 2, or combinations thereof. For example, in some embodiments, thenanowires comprise a transition metal tungstate and are doped withlithium. In other embodiments, the nanowires comprise a transition metaltungstate and are doped with sodium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with potassium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with rubidium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with caesium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with beryllium. In other embodiments, the nanowirescomprise a transition metal tungstate and are doped with magnesium. Inother embodiments, the nanowires comprise a transition metal tungstateand are doped with calcium. In other embodiments, the nanowires comprisea transition metal tungstate and are doped with strontium. In otherembodiments, the nanowires comprises a transition metal tungstate andare doped with barium.

In some embodiments the nanowires comprise Mn/Mg/O and are doped with adopant from group 1, group 2, group 7, group 8, group 9 or group 10 orcombinations thereof. For example, in some embodiments, the nanowirescomprise Mn/Mg/O and are doped with lithium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with sodium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped withpotassium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with rubidium. In other embodiments, the nanowires compriseMn/Mg/O and are doped with caesium. In other embodiments, the nanowirescomprise Mn/Mg/O and are doped with beryllium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with magnesium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped with calcium.In other embodiments, the nanowires comprise Mn/Mg/O and are doped withstrontium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with barium.

In yet some other embodiments, the nanowires comprise Mn/Mg/O and aredoped with manganese. In other embodiments, the nanowires compriseMn/Mg/O and are doped with technetium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with rhenium. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped with iron. Inother embodiments, the nanowires comprise Mn/Mg/O and are doped withruthenium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with osmium. In other embodiments, the nanowires comprise Mn/Mg/Oand are doped with cobalt. In other embodiments, the nanowires compriseMn/Mg/O and are doped with rhodium. In other embodiments, the nanowirescomprise Mn/Mg/O and are doped with iridium. In other embodiments, thenanowires comprise Mn/Mg/O and are doped with nickel. In otherembodiments, the nanowires comprise Mn/Mg/O and are doped withpalladium. In other embodiments, the nanowires comprise Mn/Mg/O and aredoped with platinum.

As noted above, the present inventors have determined that certainnanowire catalysts comprising rare earth elements (e.g., rare earthoxides) are useful as catalysts in a number of reactions, for examplethe OCM reaction. In certain embodiments the rare earth element is La,Nd, Eu, Sm, Yb, Gd or Y. In some embodiments, the rare earth element isLa. In other embodiments, the rare earth element is Nd. In otherembodiments, the rare earth element is Eu. In other embodiments, therare earth element is Sm. In other embodiments, the rare earth elementis Yb. In other embodiments, the rare earth element is Gd. In otherembodiments, the rare earth element is Y.

In certain embodiments of the nanowire catalysts comprising rare earthelements, the catalyst may further comprise a dopant selected fromalkaline earth (Group 2) elements. For example, in some embodiments thedopant is selected from Be, Mg, Ca, Sr and Ba. In other embodiments, thedopant is Be. In other embodiments, the dopant is Ca. In otherembodiments, the dopant is Sr. In other embodiments, the dopant is Ba.

In some embodiments, these rare earth compositions comprise La₂O₃,Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃, Ln1_(4-x)Ln2_(x)O₆,La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La orcombinations thereof, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4.

Further, Applicants have discovered that certain doping combinations,when combined with the above rare earth compositions, serve to enhancethe catalytic activity of the nanowires in certain catalytic reactions,for example OCM. The dopants may be present in various levels (e.g.,w/w), and the nanowires may be prepared by any number of methods.Various aspects of the above nanowires are provided in the followingparagraphs and in Tables 9-12.

In certain embodiments, the above rare earth compositions comprise astrontium dopant and at least one more additional dopant selected fromgroup 1, 4-6, 13 and lanthanides. For example, in some embodiments theadditional dopant is Hf, K, Zr, Ce, Tb, Pr, W, Rb, Ta, B or combinationsthereof. In other embodiments, the dopant comprises Sr/Hf, Sr/Hf/K,Sr/Zr, Sr/Zr/K, Sr/Ce, Sr/Ce/K, Sr/Tb, Sr/Tb/K, Sr/Pr, Sr/Pr/K, Sr/W,Sr/Hf/Rb, Sr/Ta or Sr/B. In some other embodiments, the foregoing rareearth nanowires comprise La₂O₃ or La₃NdO₆.

In other embodiments, the nanowire catalysts comprise a rare earth oxideand dopants selected from at least one of the following combinationsEu/Na, Sr/Na, Mg/Na, Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf,Ca/Cs, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca,Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W,Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag,Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce,Li/Sr, Cs/Zn, Dy/K, La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy,Mg/K, Zr/K, Li/Cs, Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce,Ba/Ta, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au,Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.

In still other embodiments, the nanowire catalysts comprise a rare earthoxide and dopants selected from at least one of the followingcombinations La/Nd, La/Sm, La/Ce, La/Sr, Eu/Na, Eu/Gd, Ca/Na, Eu/Sm,Eu/Sr, Mg/Sr, Ce/Mg, Gd/Sm, Sr/W, Sr/Ta, Au/Re, Au/Pb, Bi/Hf, Sr/Sn orMg/N, Ca/S, Rb/S, Sr/Nd, Eu/Y, Mg/Nd, Sr/Na, Nd/Mg, La/Mg, Yb/S, Mg/Na,Sr/W, K/La, K/Na, Li/Cs, Li/Na, Zn/K, Li/K, Rb/Hf, Ca/Cs, Hf/Bi, Sr/Sn,Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf,Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn,Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au,Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Zr/Cs, Ca/Ce, Li/Sr, Cs/Zn, Dy/K,La/Mg, In/Sr, Sr/Cs, Ga/Cs, Lu/Fe, Sr/Tm, La/Dy, Mg/K, Zr/K, Li/Cs,Sm/Cs, In/K, Lu/Tl, Pr/Zn, Lu/Nb, Na/Pt, Na/Ce, Ba/Ta, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho,Zr/Bi, Ho/Sr, Ca/Sr, Sr/Pb and Sr/Hf.

In other embodiments of the foregoing rare earth oxide nanowirecatalysts, the nanowire catalysts comprise a combination of two dopingelements. In some embodiments, the combination of two doping elements isLa/Nd. In other embodiments, the combination of two doping elements isLa/Sm. In other embodiments, the combination of two doping elements isLa/Ce. In other embodiments, the combination of two doping elements isLa/Sr. In other embodiments, the combination of two doping elements isEu/Na. In other embodiments, the combination of two doping elements isEu/Gd. In other embodiments, the combination of two doping elements isCa/Na. In other embodiments, the combination of two doping elements isEu/Sm. In other embodiments, the combination of two doping elements isEu/Sr. In other embodiments, the combination of two doping elements isMg/Sr. In other embodiments, the combination of two doping elements isCe/Mg. In other embodiments, the combination of two doping elements isGd/Sm. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isSr/Ta. In other embodiments, the combination of two doping elements isAu/Re. In other embodiments, the combination of two doping elements isAu/Pb. In other embodiments, the combination of two doping elements isBi/Hf. In other embodiments, the combination of two doping elements isSr/Sn. In other embodiments, the combination of two doping elements isMg/N. In other embodiments, the combination of two doping elements isCa/S. In other embodiments, the combination of two doping elements isRb/S. In other embodiments, the combination of two doping elements isSr/Nd. In other embodiments, the combination of two doping elements isEu/Y. In other embodiments, the combination of two doping elements isMg/Nd. In other embodiments, the combination of two doping elements isSr/Na. In other embodiments, the combination of two doping elements isNd/Mg. In other embodiments, the combination of two doping elements isLa/Mg. In other embodiments, the combination of two doping elements isYb/S. In other embodiments, the combination of two doping elements isMg/Na. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isK/La. In other embodiments, the combination of two doping elements isK/Na. In other embodiments, the combination of two doping elements isLi/Cs. In other embodiments, the combination of two doping elements isLi/Na. In other embodiments, the combination of two doping elements isZn/K. In other embodiments, the combination of two doping elements isLi/K. In other embodiments, the combination of two doping elements isRb/Hf. In other embodiments, the combination of two doping elements isCa/Cs. In other embodiments, the combination of two doping elements isHf/Bi. In other embodiments, the combination of two doping elements isSr/Sn. In other embodiments, the combination of two doping elements isSr/W. In other embodiments, the combination of two doping elements isSr/Nb. In other embodiments, the combination of two doping elements isZr/W. In other embodiments, the combination of two doping elements isY/W. In other embodiments, the combination of two doping elements isNa/W. In other embodiments, the combination of two doping elements isBi/W. In other embodiments, the combination of two doping elements isBi/Cs. In other embodiments, the combination of two doping elements isBi/Ca. In other embodiments, the combination of two doping elements isBi/Sn. In other embodiments, the combination of two doping elements isBi/Sb. In other embodiments, the combination of two doping elements isGe/Hf. In other embodiments, the combination of two doping elements isHf/Sm. In other embodiments, the combination of two doping elements isSb/Ag. In other embodiments, the combination of two doping elements isSb/Bi. In other embodiments, the combination of two doping elements isSb/Au. In other embodiments, the combination of two doping elements isSb/Sm. In other embodiments, the combination of two doping elements isSb/Sr. In other embodiments, the combination of two doping elements isSb/W. In other embodiments, the combination of two doping elements isSb/Hf. In other embodiments, the combination of two doping elements isSb/Yb. In other embodiments, the combination of two doping elements isSb/Sn. In other embodiments, the combination of two doping elements isYb/Au. In other embodiments, the combination of two doping elements isYb/Ta. In other embodiments, the combination of two doping elements isYb/W. In other embodiments, the combination of two doping elements isYb/Sr. In other embodiments, the combination of two doping elements isYb/Pb. In other embodiments, the combination of two doping elements isYb/W. In other embodiments, the combination of two doping elements isYb/Ag. In other embodiments, the combination of two doping elements isAu/Sr. In other embodiments, the combination of two doping elements isW/Ge. In other embodiments, the combination of two doping elements isTa/Hf. In other embodiments, the combination of two doping elements isW/Au. In other embodiments, the combination of two doping elements isCa/W. In other embodiments, the combination of two doping elements isAu/Re. In other embodiments, the combination of two doping elements isSm/Li. In other embodiments, the combination of two doping elements isLa/K. In other embodiments, the combination of two doping elements isZn/Cs. In other embodiments, the combination of two doping elements isZr/Cs. In other embodiments, the combination of two doping elements isCa/Ce. In other embodiments, the combination of two doping elements isLi/Sr. In other embodiments, the combination of two doping elements isCs/Zn. In other embodiments, the combination of two doping elements isDy/K. In other embodiments, the combination of two doping elements isLa/Mg. In other embodiments, the combination of two doping elements isIn/Sr. In other embodiments, the combination of two doping elements isSr/Cs. In other embodiments, the combination of two doping elements isGa/Cs. In other embodiments, the combination of two doping elements isLu/Fe. In other embodiments, the combination of two doping elements isSr/Tm. In other embodiments, the combination of two doping elements isLa/Dy. In other embodiments, the combination of two doping elements isMg/K. In other embodiments, the combination of two doping elements isZr/K. In other embodiments, the combination of two doping elements isLi/Cs. In other embodiments, the combination of two doping elements isSm/Cs. In other embodiments, the combination of two doping elements isIn/K. In other embodiments, the combination of two doping elements isLu/Tl. In other embodiments, the combination of two doping elements isPr/Zn. In other embodiments, the combination of two doping elements isLu/Nb. In other embodiments, the combination of two doping elements isNa/Pt. In other embodiments, the combination of two doping elements isNa/Ce. In other embodiments, the combination of two doping elements isBa/Ta. In other embodiments, the combination of two doping elements isCu/Sn. In other embodiments, the combination of two doping elements isAg/Au. In other embodiments, the combination of two doping elements isAl/Bi. In other embodiments, the combination of two doping elements isAl/Mo. In other embodiments, the combination of two doping elements isAl/Nb. In other embodiments, the combination of two doping elements isAu/Pt. In other embodiments, the combination of two doping elements isGa/Bi. In other embodiments, the combination of two doping elements isMg/W. In other embodiments, the combination of two doping elements isPb/Au. In other embodiments, the combination of two doping elements isSn/Mg. In other embodiments, the combination of two doping elements isZn/Bi. In other embodiments, the combination of two doping elements isGd/Ho. In other embodiments, the combination of two doping elements isZr/Bi. In other embodiments, the combination of two doping elements isHo/Sr. In other embodiments, the combination of two doping elements isCa/Sr. In other embodiments, the combination of two doping elements isSr/Pb. In other embodiments, the combination of two doping elements isSr/Hf.

In still other embodiments, the nanowire catalysts comprise a rare earthoxide and dopants selected from at least one of the followingcombinations Mg/La/K, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/K, K/La/S,Li/Cs/La, Li/Sr/Cs, Li/Ga/Cs, Li/Na/Sr, Li/Sm/Cs, Cs/K/La, Sr/Cs/La,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Rb/Sr/Lu, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi,Ca/Mg/Na, Na/K/Mg, Na/Li/Cs, La/Dy/K, Sm/Li/Sr, Li/Rb/Ga, Li/Cs/Tm,Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Cs/La/Na, La/S/Sr, Rb/Sr/La,Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K, Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta,Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta, Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W,Na/Zr/Eu/Tm, Sr/W/Li, Ca/Sr/W or Mg/Nd/Fe.

In more embodiments, the nanowire catalysts comprise a rare earth oxideand dopants selected from at least one of the following combinationsNd/Sr/CaO, La/Nd/Sr, La/Bi/Sr, Mg/Nd/Fe, Mg/La/K, Na/Dy/K, Na/La/Dy,Na/La/Eu, Na/La/K, K/La/S, Li/Cs/La, Li/Sr/Cs, Li/Ga/Cs, Li/Na/Sr,Li/Sm/Cs, Cs/K/La, Sr/Cs/La, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Rb/Sr/Lu,Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Ca/Mg/Na, Na/K/Mg, Na/Li/Cs, La/Dy/K,Sm/Li/Sr, Li/Rb/Ga, Li/Cs/Tm, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La,Cs/La/Na, La/S/Sr, Rb/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, La/Dy/Gd, Gd/Li/K,Rb/K/Lu, Na/Ce/Co, Ba/Rh/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb, Hf/Zr/Ta,Na/Ca/Lu, Gd/Ho/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/W/Li or Ca/Sr/W.

In other embodiments of the foregoing rare earth oxide nanowirecatalysts, the nanowire catalysts comprise a combination of at leastthree doping elements. In some embodiments, the combination of at leastthree different doping elements is Nd/Sr/CaO. In other embodiments, thecombination of at least three different doping elements is La/Nd/Sr. Inother embodiments, the combination of at least three different dopingelements is La/Bi/Sr. In other embodiments, the combination of at leastthree different doping elements is Mg/Nd/Fe. In other embodiments, thecombination of at least three different doping elements is Mg/La/K. Inother embodiments, the combination of at least three different dopingelements is Na/Dy/K. In other embodiments, the combination of at leastthree different doping elements is Na/La/Dy. In other embodiments, thecombination of at least three different doping elements is Na/La/Eu. Inother embodiments, the combination of at least three different dopingelements is Na/La/K. In other embodiments, the combination of at leastthree different doping elements is K/La/S. In other embodiments, thecombination of at least three different doping elements is Li/Cs/La. Inother embodiments, the combination of at least three different dopingelements is Li/Sr/Cs. In other embodiments, the combination of at leastthree different doping elements is Li/Ga/Cs. In other embodiments, thecombination of at least three different doping elements is Li/Na/Sr. Inother embodiments, the combination of at least three different dopingelements is Li/Sm/Cs. In other embodiments, the combination of at leastthree different doping elements is Cs/K/La. In other embodiments, thecombination of at least three different doping elements is Sr/Cs/La. Inother embodiments, the combination of at least three different dopingelements is Sr/Ho/Tm. In other embodiments, the combination of at leastthree different doping elements is La/Nd/S. In other embodiments, thecombination of at least three different doping elements is Li/Rb/Ca. Inother embodiments, the combination of at least three different dopingelements is Rb/Sr/Lu. In other embodiments, the combination of at leastthree different doping elements is Na/Eu/Hf. In other embodiments, thecombination of at least three different doping elements is Dy/Rb/Gd. Inother embodiments, the combination of at least three different dopingelements is Na/Pt/Bi. In other embodiments, the combination of at leastthree different doping elements is Ca/Mg/Na. In other embodiments, thecombination of at least three different doping elements is Na/K/Mg. Inother embodiments, the combination of at least three different dopingelements is Na/Li/Cs. In other embodiments, the combination of at leastthree different doping elements is La/Dy/K. In other embodiments, thecombination of at least three different doping elements is Sm/Li/Sr. Inother embodiments, the combination of at least three different dopingelements is Li/Rb/Ga. In other embodiments, the combination of at leastthree different doping elements is Li/Cs/Tm. In other embodiments, thecombination of at least three different doping elements is Li/K/La. Inother embodiments, the combination of at least three different dopingelements is Ce/Zr/La. In other embodiments, the combination of at leastthree different doping elements is Ca/Al/La. In other embodiments, thecombination of at least three different doping elements is Sr/Zn/La. Inother embodiments, the combination of at least three different dopingelements is Cs/La/Na. In other embodiments, the combination of at leastthree different doping elements is La/S/Sr. In other embodiments, thecombination of at least three different doping elements is Rb/Sr/La. Inother embodiments, the combination of at least three different dopingelements is Na/Sr/Lu. In other embodiments, the combination of at leastthree different doping elements is Sr/Eu/Dy. In other embodiments, thecombination of at least three different doping elements is La/Dy/Gd. Inother embodiments, the combination of at least three different dopingelements is Gd/Li/K. In other embodiments, the combination of at leastthree different doping elements is Rb/K/Lu. In other embodiments, thecombination of at least three different doping elements is Na/Ce/Co. Inother embodiments, the combination of at least three different dopingelements is Ba/Rh/Ta. In other embodiments, the combination of at leastthree different doping elements is Na/Al/Bi. In other embodiments, thecombination of at least three different doping elements is Cs/Eu/S. Inother embodiments, the combination of at least three different dopingelements is Sm/Tm/Yb. In other embodiments, the combination of at leastthree different doping elements is Hf/Zr/Ta. In other embodiments, thecombination of at least three different doping elements is Na/Ca/Lu. Inother embodiments, the combination of at least three different dopingelements is Gd/Ho/Sr. In other embodiments, the combination of at leastthree different doping elements is Ca/Sr/W. In other embodiments, thecombination of at least three different doping elements is Na/Zr/Eu/Tm.In other embodiments, the combination of at least three different dopingelements is Sr/W/Li. In other embodiments, the combination of at leastthree different doping elements is Ca/Sr/W.

As noted above, certain doping combinations have been found useful invarious catalytic reactions, such as OCM. Thus, in one embodiment, thecatalytic nanowire comprises a combination of at least four differentdoping elements, wherein the doping elements are selected from a metalelement, a semi-metal element and a non-metal element. For example incertain embodiments the catalytic nanowire comprises a metal oxide, andin other embodiments the catalytic nanowire comprises a lanthanidemetal. Still other embodiments provide a catalytic nanowire comprisingLa₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃ or combinationsthereof. In still other embodiments, the doping elements do not includeat least one of Li, B, Na, Co or Ga, and in other embodiments thenanowires do not comprise Mg and/or Mn.

In other embodiments, the catalytic nanowire comprises a lanthanideoxide, for example a lanthanide mixed oxide, for example in someembodiments the catalytic nanowire comprises Ln1_(4-x)Ln2_(x)O₆, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4. In other embodiments, the catalytic nanowire comprisesLa_(4-x)Nd_(x)O₆, wherein x is a number ranging from greater than 0 toless than 4, and in still other embodiments, the catalytic nanowirecomprises La₃NdO₆, LaNd₃O₆, La_(1.6)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.6)Nd_(0.6)O₆, La_(3.8)Nd_(0.2)O₆ orcombinations thereof. In certain other embodiments the mixed oxidecomprises Y—La, Zr—La, Pr—La, Ce—La or combinations thereof.

In other embodiments, the doping elements are selected from Eu, Na, Sr,Ca, Mg, Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni,Lu, Ta, P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe,Al, Zr, Tl, Pr, Co, Ce, Rh, and Mo. For example, in some embodiments,the combination of at least four different doping elements is:Na/Zr/Eu/Ca, Sr/Sm/Ho/Tm, Na/K/Mg/Tm, Na/La/Eu/In, Na/La/Li/Cs,Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/K/Sr/La, Li/Na/Rb/Ga,Li/Na/Sr/La, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/La/Tm/Na,Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Tm/Li/Cs, Zr/Cs/K/La, Rb/Ca/In/Ni,Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Na/Sr/Lu/Nb, Na/Nd/In/K,Rb/Ga/Tm/Cs, K/La/Zr/Ag, Ho/Cs/Li/La, K/La/Zr/Ag, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Mg/Tl/P, Sr/La/Dy/S, Na/Ga/Gd/Al, Sm/Tm/Yb/Fe,Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Zr/Eu/Tm Sr/Ho/Tm/Na or Rb/Ga/Tm/Cs orLa/Bi/Ce/Nd/Sr.

In other embodiments, the combination of at least four different dopingelements is Sr/Sm/Ho/Tm. In other embodiments, the combination of atleast four different doping elements is Na/K/Mg/Tm. In otherembodiments, the combination of at least four different doping elementsis Na/La/Eu/In. In other embodiments, the combination of at least fourdifferent doping elements is Na/La/Li/Cs. In other embodiments, thecombination of at least four different doping elements is Li/Cs/La/Tm.In other embodiments, the combination of at least four different dopingelements is Li/Cs/Sr/Tm. In other embodiments, the combination of atleast four different doping elements is Li/Sr/Zn/K. In otherembodiments, the combination of at least four different doping elementsis Li/Ga/Cs. In other embodiments, the combination of at least fourdifferent doping elements is Li/K/Sr/La. In other embodiments, thecombination of at least four different doping elements is Li/Na/Rb/Ga.In other embodiments, the combination of at least four different dopingelements is Li/Na/Sr/La. In other embodiments, the combination of atleast four different doping elements is Ba/Sm/Yb/S. In otherembodiments, the combination of at least four different doping elementsis Ba/Tm/K/La. In other embodiments, the combination of at least fourdifferent doping elements is Ba/Tm/Zn/K. In other embodiments, thecombination of at least four different doping elements is Cs/La/Tm/Na.In other embodiments, the combination of at least four different dopingelements is Cs/Li/K/La. In other embodiments, the combination of atleast four different doping elements is Sm/Li/Sr/Cs. In otherembodiments, the combination of at least four different doping elementsis Sr/Tm/Li/Cs. In other embodiments, the combination of at least fourdifferent doping elements is Zr/Cs/K/La. In other embodiments, thecombination of at least four different doping elements is Rb/Ca/In/Ni.In other embodiments, the combination of at least four different dopingelements is Tm/Lu/Ta/P. In other embodiments, the combination of atleast four different doping elements is Rb/Ca/Dy/P. In otherembodiments, the combination of at least four different doping elementsis Mg/La/Yb/Zn. In other embodiments, the combination of at least fourdifferent doping elements is Na/Sr/Lu/Nb. In other embodiments, thecombination of at least four different doping elements is Na/Nd/In/K. Inother embodiments, the combination of at least four different dopingelements is K/La/Zr/Ag. In other embodiments, the combination of atleast four different doping elements is Ho/Cs/Li/La. In otherembodiments, the combination of at least four different doping elementsis K/La/Zr/Ag. In other embodiments, the combination of at least fourdifferent doping elements is Na/Sr/Eu/Ca. In other embodiments, thecombination of at least four different doping elements is K/Cs/Sr/La. Inother embodiments, the combination of at least four different dopingelements is Na/Mg/Tl/P. In other embodiments, the combination of atleast four different doping elements is Sr/La/Dy/S. In otherembodiments, the combination of at least four different doping elementsis Na/Ga/Gd/Al. In other embodiments, the combination of at least fourdifferent doping elements is Sm/Tm/Yb/Fe. In other embodiments, thecombination of at least four different doping elements is Rb/Gd/Li/K. Inother embodiments, the combination of at least four different dopingelements is Gd/Ho/Al/P. In other embodiments, the combination of atleast four different doping elements is Na/Zr/Eu/T. In otherembodiments, the combination of at least four different doping elementsis Sr/Ho/Tm/Na. In other embodiments, the combination of at least fourdifferent doping elements is Na/Zr/Eu/Ca. In other embodiments, thecombination of at least four different doping elements is Rb/Ga/Tm/Cs.In other embodiments, the combination of at least four different dopingelements is La/Bi/Ce/Nd/Sr.

In other embodiments, the catalytic nanowire comprises at least twodifferent doping elements, wherein the doping elements are selected froma metal element, a semi-metal element and a non-metal element, andwherein at least one of the doping elements is K, Sc, Ti, V, Nb, Ru, Os,Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an elementselected from any of groups 6, 7, 10, 11, 14, 15 or 17. In someembodiments, at least one of the doping elements is K, Ti, V, Nb, Ru,Os, Ir, Cd, In, Tl, S, Se, Po, Pr, Tb, Dy, Ho, Er, Tm, Lu or an elementselected from any of groups 10, 11, 14, 15 or 17. In certain otherembodiments of the foregoing catalytic nanowire, the catalytic nanowirecomprises a metal oxide, and in other embodiments the catalytic nanowirecomprises a lanthanide metal. In still other embodiments the catalyticnanowire comprises La₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃or combinations thereof.

In other embodiments of the foregoing catalytic nanowire, the catalyticnanowire comprises a lanthanide oxide, for example a lanthanide mixedoxide, for example in some embodiments the catalytic nanowire comprisesLn1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4. In other embodiments,the catalytic nanowire comprises La_(4-x)Nd_(x)O₆, wherein x is a numberranging from greater than 0 to less than 4, and in still otherembodiments, the catalytic nanowire comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ or combinations thereof. Incertain other embodiments the mixed oxide comprises Y—La, Zr—La, Pr—La,Ce—La or combinations thereof.

In other embodiments of the nanowire comprising at least two dopingelements, the doping elements are selected from Eu, Na, Sr, Ca, Mg, Sm,Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta, P,Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl,Pr, Co, Ce, Rh, and Mo.

In yet another aspect, the present disclosure provides a catalyticnanowire comprising at least one of the following dopant combinations:Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K,Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K,Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S,Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf,Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au,Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr,Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li,La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag,Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm,Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs,In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn,Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In other embodiments of the foregoing catalytic nanowire, the dopant isselected from Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi,Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr,Ca/Sr/W, Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Ca, Sr/W/Li, Ca/Sr/W, Sr/Hf,Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K,Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/Eu/In, Na/La/K,Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga and Li/Na/Sr.

In still other embodiments of the foregoing catalytic nanowire thedopant is selected from Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La,Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca,Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta,Ba/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K,Gd/Ho/Al/P and Na/Ca/Lu.

In still other embodiments of the foregoing catalytic nanowire, thedopant is selected from Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs,Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg,Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca,K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt,Gd/Li/K, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga,Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs,Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K,Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf,Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb,Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag,Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta,Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr and W/Ge.

For example in certain embodiments of the foregoing catalytic nanowire,the catalytic nanowire comprises a metal oxide, and in other embodimentsthe catalytic nanowire comprises a lanthanide metal. In still otherembodiments, the catalytic nanowire comprises La₂O₃, Nd₂O₃, Yb₂O₃,Eu₂O₃, Sm₂O₃, Y₂O₃, Ce₂O₃, Pr₂O₃ or combinations thereof.

In other embodiments of the foregoing nanowire, the catalytic nanowirecomprises a lanthanide oxide, for example a lanthanide mixed oxide, forexample in some embodiments the catalytic nanowire comprisesLn1_(4-x)Ln2_(x)O₆, wherein Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4. In other embodiments,the catalytic nanowire comprises La_(4-x)Nd_(x)O₆, wherein x is a numberranging from greater than 0 to less than 4, and in still otherembodiments, the catalytic nanowire comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ or combinations thereof. Incertain other embodiments the mixed oxide comprises Y—La, Zr—La, Pr—La,Ce—La or combinations thereof.

In still other embodiments, the disclosure provides a catalytic nanowirecomprising Ln1_(4-x)Ln2_(x)O₆ and a dopant comprising a metal element, asemi-metal element, a non-metal element or combinations thereof, whereinLn1 and Ln2 are each independently a lanthanide element, wherein Ln1 andLn2 are not the same and x is a number ranging from greater than 0 toless than 4. For example, in certain embodiments the catalytic nanowirecomprises La_(4-x)Ln1_(x)O₆, wherein Ln1 is a lanthanide element and xis a number ranging from greater than 0 to less than 4, and in otherspecific embodiments, the catalytic nanowire comprises La_(4-x)Nd_(x)O₆,wherein x is a number ranging from greater than 0 to less than 4.

Still further embodiments of the foregoing nanowire include embodimentswherein the catalytic nanowire comprises comprises La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆ or combinations thereof.

In other embodiments, the dopant is selected from: Eu, Na, Sr, Ca, Mg,Sm, Ho, Tm, W, La, K, Dy, In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta,P, Hf, Tb, Gd, Pt, Bi, Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr,Tl, Pr, Co, Ce, Rh, and Mo. For example in certain embodiments, thecatalytic nanowire comprises at least one of the following dopantcombinations: Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W,Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In,Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm,Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na,Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S,Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La,Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni,Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn,Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf,Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W,Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au,Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr,Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li,La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K,Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag,Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm,Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs,In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn,Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In other embodiments, the disclosure provides a nanowire comprising amixed oxide of Y—La, Zr—La, Pr—La, Ce—La or combinations thereof and atleast one dopant selected from a metal element, a semi-metal element anda non-metal element. For example, in some embodiments the at least onedopant is selected from Eu, Na, Sr, Ca, Mg, Sm, Ho, Tm, W, La, K, Dy,In, Li, Cs, S, Zn, Ga, Rb, Ba, Yb, Ni, Lu, Ta, P, Hf, Tb, Gd, Pt, Bi,Sn, Nb, Sb, Ge, Ag, Au, Pb, B, Re, Fe, Al, Zr, Tl, Pr, Co, Ce, Rh, andMo, and in even other embodiments, the catalytic nanowire comprises atleast one of the following dopant combinations: Eu/Na, Sr/Na,Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K,Na/La/Dy, Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La,K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs,Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr,Li/Na/Sr/La, Sr/Zr, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K,Sr/Zr/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La,Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca,Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb,Na/Eu/Hf, Dy/Rb/Gd, Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi,Sr/Sn, Sr/W, Sr/Nb, Sr/Ce/K, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn,Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf,Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr,W/Ge, Sr/Tb, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg,Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K,In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm,La/Dy, Sm/Li/Sr, Mg/K, Sr/Pr, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La,Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La,Sr/Pr/K, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La,Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd,Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce,Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe,Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au,Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi,Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm,Sr/Ho/Tm/Na, Sr/Pb, Sr/W/Li, Ca/Sr/W or Sr/Hf.

In still other embodiments, the invention provides a catalytic nanowirecomprising a mixed oxide of a rare earth element and a Group 13 element,wherein the catalytic nanowire further comprises one or more Group 2elements. In some embodiments, the Group 13 element is B, Al, Ga or In.In other embodiments, the Group 2 element is Ca or Sr. In still otherembodiments, the rare earth element is La, Y, Nd, Yb, Sm, Pr, Ce or Eu.

Examples of the foregoing catalytic nanowires include catalyticnanowires comprising CaLnBO_(x), CaLnAlO_(x), CaLnGaO_(x), CaLnInO_(x),CaLnAlSrO_(x) and CaLnAlSrO_(x), wherein Ln is a lanthanide or yttriumand x is number such that all charges are balanced. For example, in someembodiments, the catalytic nanowire comprises CaLaBO₄, CaLaAlO₄,CaLaGaO₄, CaLaInO₄, CaLaAlSrO₅, CaLaAlSrO₅, CaNdBO₄, CaNdAlO₄, CaNdGaO₄,CaNdInO₄, CaNdAlSrO₄, CaNdAlSrO₄, CaYbBO₄, CaYbAlO₄, CaYbGaO₄, CaYbInO₄,CaYbAlSrO₅, CaYbAlSrO₅, CaEuBO₄, CaEuAlO₄, CaEuGaO₄, CaEuInO₄,CaEuAlSrO₅, CaEuAlSrO₅, CaSmBO₄, CaSmAlO₄, CaSmGaO₄, CaSmInO₄,CaSmAlSrO₅, CaSmAlSrO₅, CaYBO₄, CaYAlO₄, CaYGaO₄, CaYInO₄, CaYAlSrO₅,CaYAlSrO₅, CaCeBO₄, CaCeAlO₄, CaCeGaO₄, CaCeInO₄, CaCeAlSrO₅,CaCeAlSrO₅, CaPrBO₄, CaPrAlO₄, CaPrGaO₄, CaPrInO₄, CaPrAlSrO₅ orCaPrAlSrO₅.

In still other embodiments, the invention is directed to a catalyticnanowire comprising a rare earth oxide, wherein the nanowires are dopedwith a dopant (or dopants) selected from Eu/Na, Sr/Na, Na/Zr/Eu/Ca,Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy,Sr/Hf/K, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S,K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K,Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Sr/Zr,Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Sr/Zr/K, Cs/K/La,Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K,Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P,Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd,Sr/Ce, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb,Sr/Ce/K, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf,Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn,Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Sr/Tb,Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce,Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs,Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tb/K, Sr/Tm, La/Dy, Sm/Li/Sr,Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La,Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Sr/Pr/K, Cs/La/Na,La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La,Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K,Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta,Na/Al/Bi, Sr/Hf/Rb, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta,Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb,Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Sr/B, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr,Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Sr/Ho/Tm/Na, Na/Zr/Eu/Tm, Sr/Pb, Sr/W/Li,Ca/Sr/W or Sr/Hf. In one embodiment of the foregoing, nanowires compriseLa₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃, Ln1_(4-x)Ln2_(x)O₆,La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, wherein Ln1 and Ln2 are eachindependently a lanthanide element, wherein Ln1 and Ln2 are not the sameand x is a number ranging from greater than 0 to less than 4, La₃NdO₆,LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La orcombinations thereof.

In other embodiments, the nanowires comprise La₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃,Y₂O₃, Ce₂O₃, Pr₂O₃, Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆,La_(4-x)Nd_(x)O₆, wherein L_(n)1 and L_(n)2 are each independently alanthanide element, wherein L_(n)1 and L_(n)2 are not the same and x isa number ranging from greater than 0 to less than 4, La₃NdO₆, LaNd₃O₆,La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆,La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—Ladoped with Sr/Ta, for example in some embodiments the nanowires compriseSr/Ta/La₂O₃, Sr/Ta/Yb₂O₃, Sr/Ta/Eu₂O₃, Sr/Ta/Sm₂O₃, Sr/Ta/La₃NdO₆,Sr/Ta/LaNd₃O₆, Sr/Ta/La_(1.5)Nd_(2.5)O₆, Sr/Ta/La_(2.5)Nd_(1.5)O₆,Sr/Ta/La_(3.2)Nd_(0.8)O₆, Sr/Ta/La_(3.5)Nd_(0.5)O₆,Sr/Ta/La_(3.8)Nd_(0.2)O₆, Sr/Ta/Y—La, Sr/Ta/Zr—La, Sr/Ta/Pr—La orSr/Ta/Ce—La or combinations thereof. In other embodiments, the nanowirescomprise Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆,wherein Ln1 and Ln2 are each independently a lanthanide element, whereinLn1 and Ln2 are not the same and x is a number ranging from greater than0 to less than 4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆,La_(2.5)Nd_(1.5)O₆, La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆,La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La, Pr—La or Ce—La doped with Na, Sr, Ca,Yb, Cs or Sb, for example the nanowires may compriseNa/Ln1_(4-x)Ln2_(x)O₆, Sr/Ln1_(4-x)Ln2_(x)O₆, Ca/Ln1_(4-x)Ln2_(x)O₆,Yb/Ln1_(4-x)Ln2_(x)O₆, Cs/Ln1_(4-x)Ln2_(x)O₆, Sb/Ln1_(4-x)Ln2_(x)O₆,Na/La_(4-x)Ln1_(x)O₆, Na/La₃NdO₆, Sr/La_(4-x)Ln1_(x)O₆,Ca/La_(4-x)Ln1_(x)O₆, Yb/La_(4-x)Ln1_(x)O₆, Cs/La_(4-x)Ln1_(x)O₆,Sb/La_(4-x)Ln1_(x)O₆, Na/La_(4-x)Nd_(x)O₆, Sr/La_(4-x)Nd_(x)O₆,Ca/La_(4-x)Nd_(x)O₆, Yb/La_(4-x)Nd_(x)O₆, Cs La_(4-x)Nd_(x)O₆,Sb/La_(4-x)Nd_(x)O₆, Na/LaNd₃O₆, Na/La_(1.5)Nd_(2.5)O₆,Na/La_(2.5)Nd_(1.5)O₆, Na/La_(3.2)Nd_(0.8)O₆, Na/La_(3.5)Nd_(0.5)O₆,Na/La_(3.8)Nd_(0.2)O₆, Na/Y—La, Na/Zr—La, Na/Pr—La, Na/Ce—La,Sr/La₃NdO₆, Sr/LaNd₃O₆, Sr/La_(1.5)Nd_(2.5)O₆, Sr/La_(2.5)Nd_(1.5)O₆,Sr/La_(3.2)Nd_(0.8)O₆, Sr/La_(3.5)Nd_(0.5)O₆, Sr/La_(3.8)Nd_(0.2)O₆,Sr/Y—La, Sr/Zr—La, Sr/Pr—La, Sr/Ce—La, Ca/La₃NdO₆, Ca/LaNd₃O₆,Ca/La_(1.5)Nd_(2.5)O₆, Ca/La_(2.5)Nd_(1.5)O₆, Ca/La_(3.2)Nd_(0.8)O₆,Ca/La_(3.5)Nd_(0.5)O₆, Ca/La_(3.8)Nd_(0.2)O₆, Ca/Y—La, Ca/Zr—La,Ca/Pr—La, Ca/Ce—La, Yb/La₃NdO₆, Yb/LaNd₃O₆, Yb/La_(1.5)Nd_(2.5)O₆,Yb/La_(2.5)Nd_(1.5)O₆, Yb/La_(3.2)Nd_(0.8)O₆, Yb/La_(3.5)Nd_(0.5)O₆,Yb/La_(3.8)Nd_(0.2)O₆, Yb/Y—La, Yb/Zr—La, Yb/Pr—La, Yb/Ce—La, Cs/La₃NdO₆LaNd₃O₆, Cs/La_(1.5)Nd_(2.5)O₆, Cs/La_(2.5)Nd_(1.5)O₆,Cs/La_(3.2)Nd_(0.8)O₆, Cs/La_(3.5)Nd_(0.5)O₆, Cs/La_(3.8)Nd_(0.2)O₆,Cs/Y—La, Cs/Zr—La, Cs/Pr—La, Cs/Ce—La, Sb/La₃NdO₆, Sb/LaNd₃O₆,Sb/La_(1.5)Nd_(2.5)O₆, Sb/La_(2.5)Nd_(1.5)O₆, Sb/La_(3.2)Nd_(0.8)O₆,Sb/La_(3.5)Nd_(0.5)O₆, Sb/La_(3.8)Nd_(0.2)O₆, Sb/Y—La, Sb/Zr—La,Sb/Pr—La, Sb/Ce—La or combinations thereof.

Furthermore, the present inventors have discovered that lanthanideoxides doped with alkali metals and/or alkaline earth metals and atleast one other dopant selected from Groups 3-16 have desirablecatalytic properties and are useful in a variety of catalytic reactions,such as OCM. Accordingly, in one embodiment the nanowire catalystscomprise a lanthanide oxide doped with an alkali metal, an alkalineearth metal or combinations thereof, and at least one other dopant fromgroups 3-16. In some embodiments, the nanowire catalyst comprises alanthanide oxide, an alkali metal dopant and at least one other dopantselected from Groups 3-16. In other embodiments, the nanowire catalystcomprises a lanthanide oxide, an alkaline earth metal dopant and atleast one other dopant selected from Groups 3-16.

In some more specific embodiments of the foregoing, the nanowirecatalyst comprises a lanthanide oxide, a lithium dopant and at least oneother dopant selected from Groups 3-16. In still other embodiments, thenanowire catalyst comprises a lanthanide oxide, a sodium dopant and atleast one other dopant selected from Groups 3-16. In other embodiments,the nanowire catalyst comprises a lanthanide oxide, a potassium dopantand at least one other dopant selected from Groups 3-16. In otherembodiments, the nanowire catalyst comprises a lanthanide oxide, arubidium dopant and at least one other dopant selected from Groups 3-16.In more embodiments, the nanowire catalyst comprises a lanthanide oxide,a caesium dopant and at least one other dopant selected from Groups3-16.

In still other embodiments of the foregoing, the nanowire catalystcomprises a lanthanide oxide, a beryllium dopant and at least one otherdopant selected from Groups 3-16. In other embodiments, the nanowirecatalyst comprises a lanthanide oxide, a magnesium dopant and at leastone other dopant selected from Groups 3-16. In still other embodiments,the nanowire catalyst comprises a lanthanide oxide, a calcium dopant andat least one other dopant selected from Groups 3-16. In moreembodiments, the nanowire catalyst comprises a lanthanide oxide, astrontium dopant and at least one other dopant selected from Groups3-16. In more embodiments, the nanowire catalyst comprises a lanthanideoxide, a barium dopant and at least one other dopant selected fromGroups 3-16.

In some embodiments of the foregoing lanthanide oxide nanowirecatalysts, the catalysts comprise La₂O₃, Nd₂O₃, Yb₂O₃, Eu₂O₃, Sm₂O₃,Ln1_(4-x)Ln2_(x)O₆, La_(4-x)Ln1_(x)O₆, La_(4-x)Nd_(x)O₆, wherein Ln1 andLn2 are each independently a lanthanide element, wherein Ln1 and Ln2 arenot the same and x is a number ranging from greater than 0 to less than4, La₃NdO₆, LaNd₃O₆, La_(1.5)Nd_(2.5)O₆, La_(2.5)Nd_(1.5)O₆,La_(3.2)Nd_(0.8)O₆, La_(3.5)Nd_(0.5)O₆, La_(3.8)Nd_(0.2)O₆, Y—La, Zr—La,Pr—La or Ce—La or combinations thereof. In other various embodiments,the lanthanide oxide nanowire catalyst comprises a C₂ selectivity ofgreater than 50% and a methane conversion of greater than 20% when thelanthanide oxide nanowire catalyst is employed as a heterogenouscatalyst in the oxidative coupling of methane at a temperature of 750°C. or less.

In various embodiments, of any of the above nanowire catalysts, thenanowire catalyst comprises a C₂ selectivity of greater than 50% and amethane conversion of greater than 20% when the nanowire catalyst isemployed as a heterogenous catalyst in the oxidative coupling of methaneat a temperature of 750° C. or less, 700° C. or less, 650° C. or less oreven 600° C. or less.

In more embodiments, of any of the above nanowire catalysts, thenanowire catalyst comprises a C₂ selectivity of greater than 50%,greater than 55%, greater than 60%, greater than 65%, greater than 70%,or even greater than 75%, and a methane conversion of greater than 20%when the nanowire catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a temperature of 750° C. or less.

In other embodiments, of any of the above catalysts, the catalystcomprises a C₂ selectivity of greater than 50%, and a methane conversionof greater than 20%, greater than 25%, greater than 30%, greater than35%, greater than 40%, greater than 45%, or even greater than 50% whenthe rare earth oxide catalyst is employed as a heterogenous catalyst inthe oxidative coupling of methane at a temperature of 750° C. or less.In some embodiments of the foregoing, the methan conversion and C2selectivity are calculated based on a single pass basis (i.e., thepercent of methane converted or C2 selectivity upon a single pass overthe catalyst or catalytic bed, etc.)

In some embodiments, the foregoing doped nanowires comprise 1, 2, 3 orfour doping elements. In other embodiments, the nanowires comprise morethan four doping elements, for example, 5, 6, 7, 8, 9, 10 or even moredoping elements. In this regard, each dopant may be present in thenanowires (for example any of the nanowires disclosed in Tables 9-12) inup to 75% by weight. For example, in one embodiment the concentration ofa first doping element ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10%w/w. 10%-20% ww, 20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for exampleabout 1% w/w, about 2% w/w, about 3% w/w, about 4% w/w, about 5% w/w,about 6% w/w, about 7% w/w, about 8% w/w, about 9% w/w, about 10% w/w,about 11% w/w, about 12% w/w, about 13% w/w, about 14% w/w, about 15%w/w, about 16% w/w, about 17% w/w, about 18% w/w, about 19% w/w or about20% w/w.

In other embodiments, the concentration of a second doping element (whenpresent) ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww,20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12%w/w, about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about17% w/w, about 18% w/w, about 19% w/w or about 20% w/w.

In other embodiments, the concentration of a third doping element (whenpresent) ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww,20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12%w/w, about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about17% w/w, about 18% w/w, about 19% w/w or about 20% w/w.

In other embodiments, the concentration of a fourth doping element (whenpresent) ranges from 0.01% to 1% w/w, 1%-5% w/w, 5%-10% w/w. 10%-20% ww,20%-30% w/w, 30%-40% w/w or 40%-50% w/w, for example about 1% w/w, about2% w/w, about 3% w/w, about 4% w/w, about 5% w/w, about 6% w/w, about 7%w/w, about 8% w/w, about 9% w/w, about 10% w/w, about 11% w/w, about 12%w/w, about 13% w/w, about 14% w/w, about 15% w/w, about 16% w/w, about17% w/w, about 18% w/w, about 19% w/w or about 20% w/w.

In other embodiments, the concentration of the dopant is measured interms of atomic percent (at/at). In some of these embodiments, eachdopant may be present in the nanowires (for example any of the nanowiresdisclosed in Tables 1-12) in up to 75% at/at. For example, in oneembodiment the concentration of a first doping element ranges from 0.01%to 1% at/at, 1%-5% at/at, 5%-10% at/at. 10%-20% at/at, 20%-30% at/at,30%-40% at/at or 40%-50% at/at, for example about 1% at/at, about 2%at/at, about 3% at/at, about 4% at/at, about 5% at/at, about 6% at/at,about 7% at/at, about 8% at/at, about 9% at/at, about 10% at/at, about11% at/at, about 12% at/at, about 13% at/at, about 14% at/at, about 15%at/at, about 16% at/at, about 17% at/at, about 18% at/at, about 19%at/at or about 20% at/at.

In other embodiments, the concentration of a second doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

In other embodiments, the concentration of a third doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

In other embodiments, the concentration of a fourth doping element (whenpresent) ranges from 0.01% to 1% at/at, 1%-5% at/at, 5%-10% at/at.10%-20% ww, 20%-30% at/at, 30%-40% at/at or 40%-50% at/at, for exampleabout 1% at/at, about 2% at/at, about 3% at/at, about 4% at/at, about 5%at/at, about 6% at/at, about 7% at/at, about 8% at/at, about 9% at/at,about 10% at/at, about 11% at/at, about 12% at/at, about 13% at/at,about 14% at/at, about 15% at/at, about 16% at/at, about 17% at/at,about 18% at/at, about 19% at/at or about 20% at/at.

Accordingly, any of the doped nanowires described above or in Tables1-12, may comprise any of the foregoing doping concentrations.

Furthermore, different catalytic characteristics of the above dopednanowires can be varied or “tuned” based on the method used to preparethem. For example, in one embodiment the above nanowires (and thenanowires of Tables 1-12) are prepared using a biological templatingapproach, for example phage. In other embodiments, the nanowires areprepared via a hydrothermal or sol gel approach (i.e., a non-templatedapproach). Some embodiments for preparing the nanowires (e.g., rareearth nanowires) comprise preparing the nanowires directly from thecorresponding oxide or via a metal hydroxide gel approach. Such methodsare described in more detail herein and other methods are known in theart. In addition, the above dopants may be incorporated either before orafter (or combinations thereof) an optional calcination step asdescribed herein.

In other embodiments, the nanowires comprise a mixed oxide selected froma Y—La mixed oxide doped with Na. (Y ranges from 5 to 20% of Lamol/mol); a Zr—La mixed oxide doped with Na (Zr ranges from 1 to 5% ofLa mo/mol); a Pr—La mixed oxide doped with a group 1 element (Pr rangesfrom 2 to 6% of La mol/mol); and a Ce—La mixed oxide doped with a group1 element (Ce ranges from 5 to 20% of La mol/mol). As used herein, thenotation “M1-M2”, wherein M1 and M2 are each independently metals refersto a mixed metal oxide comprising the two metals. M1 and M2 may bepresent in equal or different amounts (at/at).

Some embodiments of the metal oxides disclosed herein can be in the formof oxides, oxyhydroxides, hydroxides, oxycarbonates or combinationthereof after being exposed to moisture, carbon dioxide, undergoingincomplete calcination or combination thereof.

It is contemplated that any one or more of the dopants disclosed hereincan be combined with any one of the nanowires disclosed herein to form adoped nanowire comprising one, two, three or more dopants. Tables 1-12below show exemplary doped nanowires in accordance with various specificembodiments. Dopants (Dop) are shown in the horizontal rows and basenanowire catalyst (NW) in the vertical columns for Tables 1-8, anddopants are shown in the vertical columns and base nanowire catalyst inthe horizontal rows for Tables 9-12. The resulting doped catalysts areshown in the intersecting cells in all tables. In some embodiments, thedoped nanowires shown in tables 1-12 are doped with one, two, three ormore additional dopants.

TABLE 1 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Li Na KRb Cs Be Mg Ca Li₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Li₂O Li₂O Li₂O Li₂OLi₂O Li₂O Li₂O Li₂O Na₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Na₂O Na₂O Na₂ONa₂O Na₂O Na₂O Na₂O Na₂O K₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ K₂O K₂O K₂OK₂O K₂O K₂O K₂O K₂O Rb₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Rb₂O Rb₂O Rb₂ORb₂O Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Cs₂O Cs₂OCs₂O Cs₂O Cs₂O Cs₂O Cs₂O Cs₂O BeO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ BeO BeOBeO BeO BeO BeO BeO BeO MgO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ MgO MgO MgOMgO MgO MgO MgO MgO CaO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ CaO CaO CaO CaOCaO CaO CaO CaO SrO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ SrO SrO SrO SrO SrOSrO SrO SrO BaO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ BaO BaO BaO BaO BaO BaOBaO BaO Sc₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Y₂O₃ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ La₂O₃La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ Li/ Na/ K/ Rb/ Cs/Be/ Mg/ Ca/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Pr₂O₃ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Nd₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Sm₂O₃ Sm₂O₃ Sm₂O₃Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Eu₂O₃Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Gd₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂Tb₆O₁₁ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Dy₂O₃ Dy₂O₃Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Li/ Na/ K/ Rb/ Cs/Be/ Mg/ Ca/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃Tm₂O₃ Yb₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Lu₂O₃ Lu₂O₃ Lu₂O₃Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ac₂O₃Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ Pa₂O₃ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃Pa₂O₃ PaO₂ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ PaO₂ PaO₂ PaO₂ PaO₂ PaO₂ PaO₂PaO₂ PaO₂ TiO₂ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ TiO₂ TiO₂ TiO₂ TiO₂ TiO₂TiO₂ TiO₂ TiO₂ TiO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ TiO TiO TiO TiO TiOTiO TiO TiO Ti₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ti₃O Ti₃OTi₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ti₂OTi₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Li/ Na/ K/ Rb/ Cs/Be/ Mg/ Ca/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Li/ Na/K/ Rb/ Cs/ Be/ Mg/ Ca/ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ VOLi/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ VO VO VO VO VO VO VO VO V₂O₃ Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ Li/ Na/K/ Rb/ Cs/ Be/ Mg/ Ca/ VO₂ VO₂ VO₂ VO₂ VO₂ VO₂ VO₂ VO₂ V₂O₅ Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Li/ Na/K/ Rb/ Cs/ Be/ Mg/ Ca/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃V₆O₁₃ NbO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ NbO NbO NbO NbO NbO NbO NbO NbONbO₂ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂NbO₂ Nb₂O₅ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₂O₂₉ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Ta₂O₅ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅Ta₂O₅ Ta₂O₅ CrO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ CrO CrO CrO CrO CrO CrOCrO CrO Cr₂O₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ CrO₂ CrO₂CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ CrO₃CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Li/ Na/K/ Rb/ Cs/ Be/ Mg/ Ca/ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂WoO₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃WoO₃ MnO Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ MnO MnO MnO MnO MnO MnO MnO MnOMn/Mg/O Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/OMn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Li/ Na/ K/ Rb/ Cs/Be/ Mg/ Ca/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Li/ Na/K/ Rb/ Cs/ Be/ Mg/ Ca/ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ Mn₂O₇ Li/Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ ReO₂ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₂ ReO₂ReO₂ ReO₂ ReO₃ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ ReO₃ ReO₃ ReO₃ ReO₃ ReO₃ReO₃ ReO₃ ReO₃ Re₂O₇ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Re₂O₇ Re₂O₇ Re₂O₇Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃— Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/B₂O₁₀ Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃—B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ Mg₃(BO₃)₂ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ NaWO₄NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈(Li,Mg)₆— Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ MnO₈ (Li,Mg)₆— (Li,Mg)₆—(Li,Mg)₆— (Li,Mg)₆— (Li,Mg)₆— (Li,Mg)₆— (Li,Mg)₆— (Li,Mg)₆— MnO₈ MnO₈MnO₈ MnO₈ MnO₈ MnO₈ MnO₈ MnO₈ Mn₂O₄ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Mn₂O₄Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Mo₂O₈ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈Mo₂O₈ Mo₂O₈ Mn₃O₄/ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ WO₄ Mn₃O₄/ Mn₃O₄/Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ Mn₃O₄/ WO₄ WO₄ WO₄ WO₄ WO₄ WO₄ WO₄WO₄ Na₂WO₄ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈NaMnO₄—/ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ MgO NaMnO₄—/ NaMnO₄—/ NaMnO₄—/NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgO MgO MgO MgOMgO Na₁₀Mn— Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ W₅O₁₇ Na₁₀Mn— Na₁₀Mn— Na₁₀Mn—Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇W₅O₁₇ W₅O₁₇ W₅O₁₇ La₃NdO₆ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ La₃NdO₆ La₃NdO₆La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆ Li/ Na/ K/ Rb/Cs/ Be/ Mg/ Ca/ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ Y—La Li/ Na/ K/ Rb/ Cs/ Be/ Mg/Ca/ Y—La Y—La Y—La Y—La Y—La Y—La Y—La Y—La Zr—La Li/ Na/ K/ Rb/ Cs/ Be/Mg/ Ca/ Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Pr—La Li/ Na/ K/Rb/ Cs/ Be/ Mg/ Ca/ Pr—La Pr—La Pr—La Pr—La Pr—La Pr—La Pr—La Pr—LaCe—La Li/ Na/ K/ Rb/ Cs/ Be/ Mg/ Ca/ Ce—La Ce—La Ce—La Ce—La Ce—La Ce—LaCe—La Ce—La

TABLE 2 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Sr Ba BP S F Cl Li₂O Sr/ Ba/ B/ P/ S/ F/ Cl/ Li₂O Li₂O Li₂O Li₂O Li₂O Li₂O Li₂ONa₂O Sr/ Ba/ B/ P/ S/ F/ Cl/ Na₂O Na₂O Na₂O Na₂O Na₂O Na₂O Na₂O K₂O Sr/Ba/ B/ P/ S/ F/ Cl/ K₂O K₂O K₂O K₂O K₂O K₂O K₂O Rb₂O Sr/ Ba/ B/ P/ S/ F/Cl/ Rb₂O Rb₂O Rb₂O Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O Sr/ Ba/ B/ P/ S/ F/ Cl/ Cs₂OCs₂O Cs₂O Cs₂O Cs₂O Cs₂O Cs₂O BeO Sr/ Ba/ B/ P/ S/ F/ Cl/ BeO BeO BeOBeO BeO BeO BeO MgO Sr/ Ba/ B/ P/ S/ F/ Cl/ MgO MgO MgO MgO MgO MgO MgOCaO Sr/ Ba/ B/ P/ S/ F/ Cl/ CaO CaO CaO CaO CaO CaO CaO SrO Sr/ Ba/ B/P/ S/ F/ Cl/ SrO SrO SrO SrO SrO SrO SrO BaO Sr/ Ba/ B/ P/ S/ F/ Cl/ BaOBaO BaO BaO BaO BaO BaO Sc₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Sc₂O₃ Sc₂O₃ Sc₂O₃Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ La₂O₃ La₂O₃ La₂O₃ La₂O₃La₂O₃ La₂O₃ La₂O₃ CeO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂CeO₂ CeO₂ Ce₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃Ce₂O₃ Ce₂O₃ Pr₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Pr₂O₃ Nd₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃Nd₂O₃ Nd₂O₃ Sm₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃Sm₂O₃ Sm₂O₃ Eu₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃Eu₂O₃ Eu₂O₃ Gd₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃Gd₂O₃ Gd₂O₃ Tb₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃Tb₂O₃ Tb₂O₃ TbO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂TbO₂ Tb₆O₁₁ Sr/ Ba/ B/ P/ S/ F/ Cl/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃Dy₂O₃ Dy₂O₃ Dy₂O₃ Ho₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Yb₂O₃ Yb₂O₃ Lu₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ThO₂ ThO₂ Pa₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃Pa₂O₃ Pa₂O₃ PaO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ PaO₂ PaO₂ PaO₂ PaO₂ PaO₂ PaO₂PaO₂ TiO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ TiO₂ TiO₂ TiO₂ TiO₂ TiO₂ TiO₂ TiO₂ TiOSr/ Ba/ B/ P/ S/ F/ Cl/ TiO TiO TiO TiO TiO TiO TiO Ti₂O₃ Sr/ Ba/ B/ P/S/ F/ Cl/ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O Sr/ Ba/ B/ P/S/ F/ Cl/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O Sr/ Ba/ B/ P/ S/ F/Cl/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ Sr/ Ba/ B/ P/ S/ F/ Cl/Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₄O₇ Sr/ Ba/ B/ P/ S/ F/ Cl/Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ HfO₂HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ VO Sr/ Ba/ B/ P/ S/ F/ Cl/ VO VO VO VO VOVO VO V₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃VO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ VO₂ VO₂ VO₂ VO₂ VO₂ VO₂ VO₂ V₂O₅ Sr/ Ba/ B/P/ S/ F/ Cl/ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ Sr/ Ba/ B/ P/ S/ F/Cl/ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ Sr/ Ba/ B/ P/ S/ F/ Cl/ V₄O₉V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ V₆O₁₃ V₆O₁₃V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO Sr/ Ba/ B/ P/ S/ F/ Cl/ NbO NbO NbONbO NbO NbO NbO NbO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂NbO₂ NbO₂ Nb₂O₅ Sr/ Ba/ B/ P/ S/ F/ Cl/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅Nb₂O₅ Nb₂O₅ Nb₈O₁₉ Sr/ Ba/ B/ P/ S/ F/ Cl/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Sr/ Ba/ B/ P/ S/ F/ Cl/ Nb₁₆O₃₈ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Sr/ Ba/ B/ P/ S/ F/ Cl/Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Sr/ Ba/B/ P/ S/ F/ Cl/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Ta₂O₅ Sr/ Ba/ B/ P/ S/ F/ Cl/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅Ta₂O₅ Ta₂O₅ CrO Sr/ Ba/ B/ P/ S/ F/ Cl/ CrO CrO CrO CrO CrO CrO CrOCr₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃CrO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ Sr/Ba/ B/ P/ S/ F/ Cl/ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ Sr/ Ba/ B/P/ S/ F/ Cl/ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Sr/Ba/ B/ P/ S/ F/ Cl/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ Sr/ Ba/ B/P/ S/ F/ Cl/ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ Sr/ Ba/ B/ P/ S/ F/Cl/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ WoO₂WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ WoO₃ WoO₃WoO₃ WoO₃ WoO₃ WoO₃ WoO₃ MnO Sr/ Ba/ B/ P/ S/ F/ Cl/ MnO MnO MnO MnO MnOMnO MnO Mn/Mg/O Sr/ Ba/ B/ P/ S/ F/ Cl/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/OMn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mn₃O₄ Mn₃O₄ Mn₃O₄Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mn₂O₃ Mn₂O₃ Mn₂O₃Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ MnO₂ MnO₂ MnO₂ MnO₂MnO₂ MnO₂ MnO₂ Mn₂O₇ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ ReO₂ ReO₂ ReO₂ ReO₂ ReO₂ReO₂ ReO₂ ReO₃ Sr/ Ba/ B/ P/ S/ F/ Cl/ ReO₃ ReO₃ ReO₃ ReO₃ ReO₃ ReO₃ReO₃ Re₂O₇ Sr/ Ba/ B/ P/ S/ F/ Cl/ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇Re₂O₇ Mg₃Mn₃— Sr/ Ba/ B/ P/ S/ F/ Cl/ B₂O₁₀ Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃—Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀B₂O₁₀ Mg₃(BO₃)₂ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ Sr/ Ba/ B/ P/ S/ F/ Cl/NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈ Sr/ Ba/ B/ P/ S/ F/Cl/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈Sr/ Ba/ B/ P/ S/ F/ Cl/ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ Sr/ Ba/ B/ P/S/ F/ Cl/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ Sr/ Ba/ B/P/ S/ F/ Cl/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Mo₂O₈ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈Mn₃O₄/WO₄ Sr/ Ba/ B/ P/ S/ F/ Cl/ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Sr/ Ba/ B/ P/ S/ F/ Cl/Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Sr/ Ba/ B/ P/S/ F/ Cl/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈NaMnO₄/MgO Sr/ Ba/ B/ P/ S/ F/ Cl/ NaMnO₄/MgO NaMnO₄/MgO NaMnO₄/MgONaMnO₄/MgO NaMnO₄/MgO NaMnO₄/MgO NaMnO₄/MgO Na₁₀Mn— Sr/ Ba/ B/ P/ S/ F/Cl/ W₅O₁₇ Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— W₅O₁₇W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ La₃NdO₆ Sr/ Ba/ B/ P/ S/ F/ Cl/La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ LaNd₃O₆ Sr/ Ba/B/ P/ S/ F/ Cl/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ Sr/ Ba/ B/ P/ S/ F/ Cl/ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ Sr/ Ba/ B/ P/ S/ F/ Cl/ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ Sr/ Ba/ B/ P/ S/ F/ Cl/ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/ Ba/ B/ P/ S/ F/ Cl/ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.8)Nd_(0.2)O₆ Sr/ Ba/ B/ P/ S/ F/ Cl/ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ Y—La Sr/ Ba/ B/P/ S/ F/ Cl/ Y—La Y—La Y—La Y—La Y—La Y—La Y—La Zr—La Sr/ Ba/ B/ P/ S/F/ Cl/ Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Pr—La Sr/ Ba/ B/ P/ S/F/ Cl/ Pr—La Pr—La Pr—La Pr—La Pr—La Pr—La Pr—La Ce—La Sr/ Ba/ B/ P/ S/F/ Cl/ Ce—La Ce—La Ce—La Ce—La Ce—La Ce—La Ce—La

TABLE 3 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop La Ce PrNd Pm Sm Eu Gd Li₂O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Li₂O Li₂O Li₂O Li₂OLi₂O Li₂O Li₂O Li₂O Na₂O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Na₂O Na₂O Na₂ONa₂O Na₂O Na₂O Na₂O Na₂O K₂O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ K₂O K₂O K₂OK₂O K₂O K₂O K₂O K₂O Rb₂O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Rb₂O Rb₂O Rb₂ORb₂O Rb₂O Rb₂O Rb₂O Rb₂O Cs₂O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Cs₂O Cs₂OCs₂O Cs₂O Cs₂O Cs₂O Cs₂O Cs₂O BeO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ BeOBeO BeO BeO BeO BeO BeO BeO MgO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ MgO MgOMgO MgO MgO MgO MgO MgO CaO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ CaO CaO CaOCaO CaO CaO CaO CaO SrO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ SrO SrO SrO SrOSrO SrO SrO SrO BaO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ BaO BaO BaO BaO BaOBaO BaO BaO Sc₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Sc₂O₃ Sc₂O₃ Sc₂O₃Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Sc₂O₃ Y₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Y₂O₃Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ Y₂O₃ La₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ La₂O₃ CeO₂ La/ Ce/ Pr/ Nd/ Pm/Sm/ Eu/ Gd/ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ CeO₂ Ce₂O₃ La/ Ce/ Pr/Nd/ Pm/ Sm/ Eu/ Gd/ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃ Ce₂O₃Pr₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃ Pr₂O₃Pr₂O₃ Pr₂O₃ Pr₂O₃ Nd₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Nd₂O₃ Nd₂O₃Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Nd₂O₃ Sm₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/Gd/ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Sm₂O₃ Eu₂O₃ La/ Ce/ Pr/Nd/ Pm/ Sm/ Eu/ Gd/ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃ Eu₂O₃Gd₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃ Gd₂O₃Gd₂O₃ Gd₂O₃ Gd₂O₃ Tb₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Tb₂O₃ Tb₂O₃Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ Tb₂O₃ TbO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ TbO₂ Tb₆O₁₁ La/ Ce/ Pr/ Nd/ Pm/ Sm/Eu/ Gd/ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃ Dy₂O₃Dy₂O₃ Dy₂O₃ Ho₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Ho₂O₃ Ho₂O₃ Ho₂O₃Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Ho₂O₃ Er₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Er₂O₃ Tm₂O₃ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Tm₂O₃ Yb₂O₃La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃ Yb₂O₃Yb₂O₃ Yb₂O₃ Lu₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Lu₂O₃ Lu₂O₃ Lu₂O₃Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Lu₂O₃ Ac₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Ac₂O₃ Th₂O₃ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ Th₂O₃ ThO₂ La/Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂ ThO₂Pa₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃ Pa₂O₃Pa₂O₃ Pa₂O₃ Pa₂O₃ PaO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ PaO₂ PaO₂ PaO₂PaO₂ PaO₂ PaO₂ PaO₂ PaO₂ TiO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ TiO₂ TiO₂TiO₂ TiO₂ TiO₂ TiO₂ TiO₂ TiO₂ TiO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ TiOTiO TiO TiO TiO TiO TiO TiO Ti₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Ti₂O₃Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₂O₃ Ti₃O La/ Ce/ Pr/ Nd/ Pm/ Sm/Eu/ Gd/ Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₃O Ti₂O La/ Ce/ Pr/ Nd/ Pm/Sm/ Eu/ Gd/ Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₂O Ti₃O₅ La/ Ce/ Pr/Nd/ Pm/ Sm/ Eu/ Gd/ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅ Ti₃O₅Ti₄O₇ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇ Ti₄O₇Ti₄O₇ Ti₄O₇ Ti₄O₇ ZrO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ ZrO₂ ZrO₂ ZrO₂ZrO₂ ZrO₂ ZrO₂ ZrO₂ ZrO₂ HfO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ HfO₂ HfO₂HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ HfO₂ VO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ VO VOVO VO VO VO VO VO V₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ V₂O₃ V₂O₃ V₂O₃V₂O₃ V₂O₃ V₂O₃ V₂O₃ V₂O₃ VO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ VO₂ VO₂ VO₂VO₂ VO₂ VO₂ VO₂ VO₂ V₂O₅ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ V₂O₅ V₂O₅ V₂O₅V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₂O₅ V₃O₇ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ V₃O₇ V₃O₇V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₃O₇ V₄O₉ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ V₄O₉V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₄O₉ V₆O₁₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ V₆O₁₃ NbO La/ Ce/ Pr/ Nd/ Pm/Sm/ Eu/ Gd/ NbO NbO NbO NbO NbO NbO NbO NbO NbO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/Eu/ Gd/ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ NbO₂ Nb₂O₅ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₂O₅ Nb₈O₁₉La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉Nb₈O₁₉ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Nb₁₆O₃₈Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ La/ Ce/Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₁₂O₂₉Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Nb₄₇O₁₁₆Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ La/Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅ Ta₂O₅Ta₂O₅ CrO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ CrO CrO CrO CrO CrO CrO CrOCrO Cr₂O₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃ Cr₂O₃Cr₂O₃ Cr₂O₃ Cr₂O₃ CrO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ CrO₂ CrO₂ CrO₂CrO₂ CrO₂ CrO₂ CrO₂ CrO₂ CrO₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ CrO₃ CrO₃CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ CrO₃ Cr₈O₂₁ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ Cr₈O₂₁ MoO₂ La/ Ce/ Pr/Nd/ Pm/ Sm/ Eu/ Gd/ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₂ MoO₃ La/ Ce/Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ MoO₃ W₂O₃ La/Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ W₂O₃ WoO₂La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂ WoO₂WoO₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃ WoO₃WoO₃ MnO La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ MnO MnO MnO MnO MnO MnO MnO MnOMn/Mg/O La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/OMn/Mg/O Mn/Mg/O Mn/Mg/O Mn/Mg/O Mn₃O₄ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₃O₄ Mn₂O₃ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ Mn₂O₃ MnO₂ La/Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂ MnO₂Mn₂O₇ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇ Mn₂O₇Mn₂O₇ Mn₂O₇ Mn₂O₇ ReO₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ ReO₂ ReO₂ ReO₂ReO₂ ReO₂ ReO₂ ReO₂ ReO₂ ReO₃ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ ReO₃ ReO₃ReO₃ ReO₃ ReO₃ ReO₃ ReO₃ ReO₃ Re₂O₇ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Re₂O₇ Mg₃Mn₃— La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ B₂O₁₀ Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃— Mg₃Mn₃—Mg₃Mn₃— Mg₃Mn₃— B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀ B₂O₁₀Mg₃(BO₃)₂ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ NaWO₄ Mg₆MnO₈La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈Mg₆MnO₈ Mg₆MnO₈ Mg₆MnO₈ (Li,Mg)₆MnO₈ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈(Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ (Li,Mg)₆MnO₈ Mn₂O₄ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/Gd/ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Mn₂O₄ Na₄P₂O₇ La/ Ce/ Pr/Nd/ Pm/ Sm/ Eu/ Gd/ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇ Na₄P₂O₇Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Mo₂O₈ Mo₂O₈ Mo₂O₈Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄ Mn₃O₄/WO₄Mn₃O₄/WO₄ Na₂WO₄ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Na₂WO₄ Na₂WO₄ Na₂WO₄Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/Gd/ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈ Zr₂Mo₂O₈Zr₂Mo₂O₈ NaMnO₄—/ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ MgO NaMnO₄—/ NaMnO₄—/NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ NaMnO₄—/ MgO MgO MgO MgOMgO MgO MgO MgO Na₁₀Mn— La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ W₅O₁₇ Na₁₀Mn—Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— Na₁₀Mn— W₅O₁₇ W₅O₁₇W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ W₅O₁₇ La₃NdO₆ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/Gd/ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆ La₃NdO₆LaNd₃O₆ La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La/ Ce/ Pr/ Nd/ Pm/Sm/ Eu/ Gd/ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆ La/ Ce/ Pr/ Nd/Pm/ Sm/ Eu/ Gd/ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ Y—La La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/Gd/ Y—La Y—La Y—La Y—La Y—La Y—La Y—La Y—La Zr—La La/ Ce/ Pr/ Nd/ Pm/Sm/ Eu/ Gd/ Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Zr—La Pr—La La/Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Pr—La Pr—La Pr—La Pr—La Pr—La Pr—La Pr—LaPr—La Ce—La La/ Ce/ Pr/ Nd/ Pm/ Sm/ Eu/ Gd/ Ce—La Ce—La Ce—La Ce—LaCe—La Ce—La Ce—La Ce—La

TABLE 4 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Tb Dy HoEr Tm Yb Lu In Li₂O Tb/Li₂O Dy/Li₂O Ho/Li₂O Er/Li₂O Tm/Li₂O Yb/Li₂OLu/Li₂O In/Li₂O Na₂O Tb/Na₂O Dy/Na₂O Ho/Na₂O Er/Na₂O Tm/Na₂O Yb/Na₂OLu/Na₂O In/Na₂O K₂O Tb/K₂O Dy/K₂O Ho/K₂O Er/K₂O Tm/K₂O Yb/K₂O Lu/K₂OIn/K₂O Rb₂O Tb/Rb₂O Dy/Rb₂O Ho/Rb₂O Er/Rb₂O Tm/Rb₂O Yb/Rb₂O Lu/Rb₂OIn/Rb₂O Cs₂O Tb/Cs₂O Dy/Cs₂O Ho/Cs₂O Er/Cs₂O Tm/Cs₂O Yb/Cs₂O Lu/Cs₂OIn/Cs₂O BeO Tb/BeO Dy/BeO Ho/BeO Er/BeO Tm/BeO Yb/BeO Lu/BeO In/BeO MgOTb/MgO Dy/MgO Ho/MgO Er/MgO Tm/MgO Yb/MgO Lu/MgO In/MgO CaO Tb/CaODy/CaO Ho/CaO Er/CaO Tm/CaO Yb/CaO Lu/CaO In/CaO SrO Tb/SrO Dy/SrOHo/SrO Er/SrO Tm/SrO Yb/SrO Lu/SrO In/SrO BaO Tb/BaO Dy/BaO Ho/BaOEr/BaO Tm/BaO Yb/BaO Lu/BaO In/BaO Sc₂O₃ Tb/Sc₂O₃ Dy/Sc₂O₃ Ho/Sc₂O₃Er/Sc₂O₃ Tm/Sc₂O₃ Yb/Sc₂O₃ Lu/Sc₂O₃ In/Sc₂O₃ Y₂O₃ Tb/Y₂O₃ Dy/Y₂O₃Ho/Y₂O₃ Er/Y₂O₃ Tm/Y₂O₃ Yb/Y₂O₃ Lu/Y₂O₃ In/Y₂O₃ La₂O₃ Tb/La₂O₃ Dy/La₂O₃Ho/La₂O₃ Er/La₂O₃ Tm/La₂O₃ Yb/La₂O₃ Lu/La₂O₃ In/La₂O₃ CeO₂ Tb/CeO₂Dy/CeO₂ Ho/CeO₂ Er/CeO₂ Tm/CeO₂ Yb/CeO₂ Lu/CeO₂ In/CeO₂ Ce₂O₃ Tb/Ce₂O₃Dy/Ce₂O₃ Ho/Ce₂O₃ Er/Ce₂O₃ Tm/Ce₂O₃ Yb/Ce₂O₃ Lu/Ce₂O₃ In/Ce₂O₃ Pr₂O₃Tb/Pr₂O₃ Dy/Pr₂O₃ Ho/Pr₂O₃ Er/Pr₂O₃ Tm/Pr₂O₃ Yb/Pr₂O₃ Lu/Pr₂O₃ In/Pr₂O₃Nd₂O₃ Tb/Nd₂O₃ Dy/Nd₂O₃ Ho/Nd₂O₃ Er/Nd₂O₃ Tm/Nd₂O₃ Yb/Nd₂O₃ Lu/Nd₂O₃In/Nd₂O₃ Sm₂O₃ Tb/Sm₂O₃ Dy/Sm₂O₃ Ho/Sm₂O₃ Er/Sm₂O₃ Tm/Sm₂O₃ Yb/Sm₂O₃Lu/Sm₂O₃ In/Sm₂O₃ Eu₂O₃ Tb/Eu₂O₃ Dy/Eu₂O₃ Ho/Eu₂O₃ Er/Eu₂O₃ Tm/Eu₂O₃Yb/Eu₂O₃ Lu/Eu₂O₃ In/Eu₂O₃ Gd₂O₃ Tb/Gd₂O₃ Dy/Gd₂O₃ Ho/Gd₂O₃ Er/Gd₂O₃Tm/Gd₂O₃ Yb/Gd₂O₃ Lu/Gd₂O₃ In/Gd₂O₃ Tb₂O₃ Tb/Tb₂O₃ Dy/Tb₂O₃ Ho/Tb₂O₃Er/Tb₂O₃ Tm/Tb₂O₃ Yb/Tb₂O₃ Lu/Tb₂O₃ In/Tb₂O₃ TbO₂ Tb/TbO₂ Dy/TbO₂Ho/TbO₂ Er/TbO₂ Tm/TbO₂ Yb/TbO₂ Lu/TbO₂ In/TbO₂ Tb₆O₁₁ Tb/Tb₆O₁₁Dy/Tb₆O₁₁ Ho/Tb₆O₁₁ Er/Tb₆O₁₁ Tm/Tb₆O₁₁ Yb/Tb₆O₁₁ Lu/Tb₆O₁₁ In/Tb₆O₁₁Dy₂O₃ Tb/Dy₂O₃ Dy/Dy₂O₃ Ho/Dy₂O₃ Er/Dy₂O₃ Tm/Dy₂O₃ Yb/Dy₂O₃ Lu/Dy₂O₃In/Dy₂O₃ Ho₂O₃ Tb/Ho₂O₃ Dy/Ho₂O₃ Ho/Ho₂O₃ Er/Ho₂O₃ Tm/Ho₂O₃ Yb/Ho₂O₃Lu/Ho₂O₃ In/Ho₂O₃ Er₂O₃ Tb/Er₂O₃ Dy/Er₂O₃ Ho/Er₂O₃ Er/Er₂O₃ Tm/Er₂O₃Yb/Er₂O₃ Lu/Er₂O₃ In/Er₂O₃ Tm₂O₃ Tb/Tm₂O₃ Dy/Tm₂O₃ Ho/Tm₂O₃ Er/Tm₂O₃Tm/Tm₂O₃ Yb/Tm₂O₃ Lu/Tm₂O₃ In/Tm₂O₃ Yb₂O₃ Tb/Yb₂O₃ Dy/Yb₂O₃ Ho/Yb₂O₃Er/Yb₂O₃ Tm/Yb₂O₃ Yb/Yb₂O₃ Lu/Yb₂O₃ In/Yb₂O₃ Lu₂O₃ Tb/Lu₂O₃ Dy/Lu₂O₃Ho/Lu₂O₃ Er/Lu₂O₃ Tm/Lu₂O₃ Yb/Lu₂O₃ Lu/Lu₂O₃ In/Lu₂O₃ Ac₂O₃ Tb/Ac₂O₃Dy/Ac₂O₃ Ho/Ac₂O₃ Er/Ac₂O₃ Tm/Ac₂O₃ Yb/Ac₂O₃ Lu/Ac₂O₃ In/Ac₂O₃ Th₂O₃Tb/Th₂O₃ Dy/Th₂O₃ Ho/Th₂O₃ Er/Th₂O₃ Tm/Th₂O₃ Yb/Th₂O₃ Lu/Th₂O₃ In/Th₂O₃ThO₂ Tb/ThO₂ Dy/ThO₂ Ho/ThO₂ Er/ThO₂ Tm/ThO₂ Yb/ThO₂ Lu/ThO₂ In/ThO₂Pa₂O₃ Tb/Pa₂O₃ Dy/Pa₂O₃ Ho/Pa₂O₃ Er/Pa₂O₃ Tm/Pa₂O₃ Yb/Pa₂O₃ Lu/Pa₂O₃In/Pa₂O₃ PaO₂ Tb/PaO₂ Dy/PaO₂ Ho/PaO₂ Er/PaO₂ Tm/PaO₂ Yb/PaO₂ Lu/PaO₂In/PaO₂ TiO₂ Tb/TiO₂ Dy/TiO₂ Ho/TiO₂ Er/TiO₂ Tm/TiO₂ Yb/TiO₂ Lu/TiO₂In/TiO₂ TiO Tb/TiO Dy/TiO Ho/TiO Er/TiO Tm/TiO Yb/TiO Lu/TiO In/TiOTi₂O₃ Tb/Ti₂O₃ Dy/Ti₂O₃ Ho/Ti₂O₃ Er/Ti₂O₃ Tm/Ti₂O₃ Yb/Ti₂O₃ Lu/Ti₂O₃In/Ti₂O₃ Ti₃O Tb/Ti₃O Dy/Ti₃O Ho/Ti₃O Er/Ti₃O Tm/Ti₃O Yb/Ti₃O Lu/Ti₃OIn/Ti₃O Ti₂O Tb/Ti₂O Dy/Ti₂O Ho/Ti₂O Er/Ti₂O Tm/Ti₂O Yb/Ti₂O Lu/Ti₂OIn/Ti₂O Ti₃O₅ Tb/Ti₃O₅ Dy/Ti₃O₅ Ho/Ti₃O₅ Er/Ti₃O₅ Tm/Ti₃O₅ Yb/Ti₃O₅Lu/Ti₃O₅ In/Ti₃O₅ Ti₄O₇ Tb/Ti₄O₇ Dy/Ti₄O₇ Ho/Ti₄O₇ Er/Ti₄O₇ Tm/Ti₄O₇Yb/Ti₄O₇ Lu/Ti₄O₇ In/Ti₄O₇ ZrO₂ Tb/ZrO₂ Dy/ZrO₂ Ho/ZrO₂ Er/ZrO₂ Tm/ZrO₂Yb/ZrO₂ Lu/ZrO₂ In/ZrO₂ HfO₂ Tb/HfO₂ Dy/HfO₂ Ho/HfO₂ Er/HfO₂ Tm/HfO₂Yb/HfO₂ Lu/HfO₂ In/HfO₂ VO Tb/VO Dy/VO Ho/VO Er/VO Tm/VO Yb/VO Lu/VOIn/VO V₂O₃ Tb/V₂O₃ Dy/V₂O₃ Ho/V₂O₃ Er/V₂O₃ Tm/V₂O₃ Yb/V₂O₃ Lu/V₂O₃In/V₂O₃ VO₂ Tb/VO₂ Dy/VO₂ Ho/VO₂ Er/VO₂ Tm/VO₂ Yb/VO₂ Lu/VO₂ In/VO₂ V₂O₅Tb/V₂O₅ Dy/V₂O₅ Ho/V₂O₅ Er/V₂O₅ Tm/V₂O₅ Yb/V₂O₅ Lu/V₂O₅ In/V₂O₅ V₃O₇Tb/V₃O₇ Dy/V₃O₇ Ho/V₃O₇ Er/V₃O₇ Tm/V₃O₇ Yb/V₃O₇ Lu/V₃O₇ In/V₃O₇ V₄O₉Tb/V₄O₉ Dy/V₄O₉ Ho/V₄O₉ Er/V₄O₉ Tm/V₄O₉ Yb/V₄O₉ Lu/V₄O₉ In/V₄O₉ V₆O₁₃Tb/V₆O₁₃ Dy/V₆O₁₃ Ho/V₆O₁₃ Er/V₆O₁₃ Tm/V₆O₁₃ Yb/V₆O₁₃ Lu/V₆O₁₃ In/V₆O₁₃NbO Tb/NbO Dy/NbO Ho/NbO Er/NbO Tm/NbO Yb/NbO Lu/NbO In/NbO NbO₂ Tb/NbO₂Dy/NbO₂ Ho/NbO₂ Er/NbO₂ Tm/NbO₂ Yb/NbO₂ Lu/NbO₂ In/NbO₂ Nb₂O₅ Tb/Nb₂O₅Dy/Nb₂O₅ Ho/Nb₂O₅ Er/Nb₂O₅ Tm/Nb₂O₅ Yb/Nb₂O₅ Lu/Nb₂O₅ In/Nb₂O₅ Nb₈O₁₉Tb/Nb₈O₁₉ Dy/Nb₈O₁₉ Ho/Nb₈O₁₉ Er/Nb₈O₁₉ Tm/Nb₈O₁₉ Yb/Nb₈O₁₉ Lu/Nb₈O₁₉In/Nb₈O₁₉ Nb₁₆O₃₈ Tb/Nb₁₆O₃₈ Dy/Nb₁₆O₃₈ Ho/Nb₁₆O₃₈ Er/Nb₁₆O₃₈ Tm/Nb₁₆O₃₈Yb/Nb₁₆O₃₈ Lu/Nb₁₆O₃₈ In/Nb₁₆O₃₈ Nb₁₂O₂₉ Tb/Nb₁₂O₂₉ Dy/Nb₁₂O₂₉Ho/Nb₁₂O₂₉ Er/Nb₁₂O₂₉ Tm/Nb₁₂O₂₉ Yb/Nb₁₂O₂₉ Lu/Nb₁₂O₂₉ In/Nb₁₂O₂₉Nb₄₇O₁₁₆ Tb/Nb₄₇O₁₁₆ Dy/Nb₄₇O₁₁₆ Ho/Nb₄₇O₁₁₆ Er/Nb₄₇O₁₁₆ Tm/Nb₄₇O₁₁₆Yb/Nb₄₇O₁₁₆ Lu/Nb₄₇O₁₁₆ In/Nb₄₇O₁₁₆ Ta₂O₅ Tb/Ta₂O₅ Dy/Ta₂O₅ Ho/Ta₂O₅Er/Ta₂O₅ Tm/Ta₂O₅ Yb/Ta₂O₅ Lu/Ta₂O₅ In/Ta₂O₅ CrO Tb/CrO Dy/CrO Ho/CrOEr/CrO Tm/CrO Yb/CrO Lu/CrO In/CrO Cr₂O₃ Tb/Cr₂O₃ Dy/Cr₂O₃ Ho/Cr₂O₃Er/Cr₂O₃ Tm/Cr₂O₃ Yb/Cr₂O₃ Lu/Cr₂O₃ In/Cr₂O₃ CrO₂ Tb/CrO₂ Dy/CrO₂Ho/CrO₂ Er/CrO₂ Tm/CrO₂ Yb/CrO₂ Lu/CrO₂ In/CrO₂ CrO₃ Tb/CrO₃ Dy/CrO₃Ho/CrO₃ Er/CrO₃ Tm/CrO₃ Yb/CrO₃ Lu/CrO₃ In/CrO₃ Cr₈O₂₁ Tb/Cr₈O₂₁Dy/Cr₈O₂₁ Ho/Cr₈O₂₁ Er/Cr₈O₂₁ Tm/Cr₈O₂₁ Yb/Cr₈O₂₁ Lu/Cr₈O₂₁ In/Cr₈O₂₁MoO₂ Tb/MoO₂ Dy/MoO₂ Ho/MoO₂ Er/MoO₂ Tm/MoO₂ Yb/MoO₂ Lu/MoO₂ In/MoO₂MoO₃ Tb/MoO₃ Dy/MoO₃ Ho/MoO₃ Er/MoO₃ Tm/MoO₃ Yb/MoO₃ Lu/MoO₃ In/MoO₃W₂O₃ Tb/W₂O₃ Dy/W₂O₃ Ho/W₂O₃ Er/W₂O₃ Tm/W₂O₃ Yb/W₂O₃ Lu/W₂O₃ In/W₂O₃WoO₂ Tb/WoO₂ Dy/WoO₂ Ho/WoO₂ Er/WoO₂ Tm/WoO₂ Yb/WoO₂ Lu/WoO₂ In/WoO₂WoO₃ Tb/WoO₃ Dy/WoO₃ Ho/WoO₃ Er/WoO₃ Tm/WoO₃ Yb/WoO₃ Lu/WoO₃ In/WoO₃ MnOTb/MnO Dy/MnO Ho/MnO Er/MnO Tm/MnO Yb/MnO Lu/MnO In/MnO Mn/Mg/OTb/Mn/Mg/O Dy/Mn/Mg/O Ho/Mn/Mg/O Er/Mn/Mg/O Tm/Mn/Mg/O Yb/Mn/Mg/OLu/Mn/Mg/O In/Mn/Mg/O Mn₃O₄ Tb/Mn₃O₄ Dy/Mn₃O₄ Ho/Mn₃O₄ Er/Mn₃O₄ Tm/Mn₃O₄Yb/Mn₃O₄ Lu/Mn₃O₄ In/Mn₃O₄ Mn₂O₃ Tb/Mn₂O₃ Dy/Mn₂O₃ Ho/Mn₂O₃ Er/Mn₂O₃Tm/Mn₂O₃ Yb/Mn₂O₃ Lu/Mn₂O₃ In/Mn₂O₃ MnO₂ Tb/MnO₂ Dy/MnO₂ Ho/MnO₂ Er/MnO₂Tm/MnO₂ Yb/MnO₂ Lu/MnO₂ In/MnO₂ Mn₂O₇ Tb/Mn₂O₇ Dy/Mn₂O₇ Ho/Mn₂O₇Er/Mn₂O₇ Tm/Mn₂O₇ Yb/Mn₂O₇ Lu/Mn₂O₇ In/Mn₂O₇ ReO₂ Tb/ReO₂ Dy/ReO₂Ho/ReO₂ Er/ReO₂ Tm/ReO₂ Yb/ReO₂ Lu/ReO₂ In/ReO₂ ReO₃ Tb/ReO₃ Dy/ReO₃Ho/ReO₃ Er/ReO₃ Tm/ReO₃ Yb/ReO₃ Lu/ReO₃ In/ReO₃ Re₂O₇ Tb/Re₂O₇ Dy/Re₂O₇Ho/Re₂O₇ Er/Re₂O₇ Tm/Re₂O₇ Yb/Re₂O₇ Lu/Re₂O₇ In/Re₂O₇ Mg₃Mn₃—B₂O₁₀Tb/Mg₃Mn₃—B₂O₁₀ Dy/Mg₃Mn₃—B₂O₁₀ Ho/Mg₃Mn₃—B₂O₁₀ Er/Mg₃Mn₃—B₂O₁₀Tm/Mg₃Mn₃—B₂O₁₀ Yb/Mg₃Mn₃—B₂O₁₀ Lu/Mg₃Mn₃—B₂O₁₀ In/Mg₃Mn₃—B₂O₁₀Mg₃(BO₃)₂ Tb/Mg₃(BO₃)₂ Dy/Mg₃(BO₃)₂ Ho/Mg₃(BO₃)₂ Er/Mg₃(BO₃)₂Tm/Mg₃(BO₃)₂ Yb/Mg₃(BO₃)₂ Lu/Mg₃(BO₃)₂ In/Mg₃(BO₃)₂ NaWO₄ Tb/NaWO₄Dy/NaWO₄ Ho/NaWO₄ Er/NaWO₄ Tm/NaWO₄ Yb/NaWO₄ Lu/NaWO₄ In/NaWO₄ Mg₆MnO₈Tb/Mg₆MnO₈ Dy/Mg₆MnO₈ Ho/Mg₆MnO₈ Er/Mg₆MnO₈ Tm/Mg₆MnO₈ Yb/Mg₆MnO₈Lu/Mg₆MnO₈ In/Mg₆MnO₈ Mn₂O₄ Tb/Mn₂O₄ Dy/Mn₂O₄ Ho/Mn₂O₄ Er/Mn₂O₄ Tm/Mn₂O₄Yb/Mn₂O₄ Lu/Mn₂O₄ In/Mn₂O₄ (Li,Mg)₆MnO₈ Tb/(Li,Mg)₆MnO₈ Dy/(Li,Mg)₆MnO₈Ho/(Li,Mg)₆MnO₈ Er/(Li,Mg)₆MnO₈ Tm/(Li,Mg)₆MnO₈ Yb/(Li,Mg)₆MnO₈Lu/(Li,Mg)₆MnO₈ In/(Li,Mg)₆MnO₈ Na₄P₂O₇ Tb/Na₄P₂O₇ Dy/Na₄P₂O₇ Ho/Na₄P₂O₇Er/Na₄P₂O₇ Tm/Na₄P₂O₇ Yb/Na₄P₂O₇ Lu/Na₄P₂O₇ In/Na₄P₂O₇ Mo₂O₈ Tb/Mo₂O₈Dy/Mo₂O₈ Ho/Mo₂O₈ Er/Mo₂O₈ Tm/Mo₂O₈ Yb/Mo₂O₈ Lu/Mo₂O₈ In/Mo₂O₈ Mn₃O₄/WO₄Tb/Mn₃O₄/WO₄ Dy/MnO₄/WO₄ Ho/Mn₃O₄/WO₄ Er/Mn₃O₄/WO₄ Tm/Mn₃O₄/WO₄Yb/Mn₃O₄/WO₄ Lu/Mn₃O₄/WO₄ In/Mn₃O₄/WO₄ Na₂WO₄ Tb/Na₂WO₄ Dy/Na₂WO₄Ho/Na₂WO₄ Er/Na₂WO₄ Tm/Na₂WO₄ Yb/Na₂WO₄ Lu/Na₂WO₄ In/Na₂WO₄ Zr₂Mo₂O₈Tb/Zr₂Mo₂O₈ Dy/Zr₂Mo₂O₈ Ho/Zr₂Mo₂O₈ Er/Zr₂Mo₂O₈ Tm/Zr₂Mo₂O₈ Yb/Zr₂Mo₂O₈Lu/Zr₂Mo₂O₈ In/Zr₂Mo₂O₈ NaMnO₄—/MgO Tb/NaMnO₄—/MgO Dy/NaMnO₄—/MgOHo/NaMnO₄—/MgO Er/NaMnO₄—/MgO Tm/NaMnO₄—/MgO Yb/NaMnO₄—/MgOLu/NaMnO₄—/MgO In/NaMnO₄—/MgO Na₁₀Mn—W₅O₁₇ Tb/Na₁₀Mn—W₅O₁₇Dy/Na₁₀Mn—W₅O₁₇ Ho/Na₁₀Mn—W₅O₁₇ Er/Na₁₀Mn—W₅O₁₇ Tm/Na₁₀Mn—W₅O₁₇Yb/Na₁₀Mn—W₅O₁₇ Lu/Na₁₀Mn—W₅O₁₇ In/Na₁₀Mn—W₅O₁₇ La₃NdO₆ Tb/La₃NdO₆Dy/La₃NdO₆ Ho/La₃NdO₆ Er/La₃NdO₆ Tm/La₃NdO₆ Yb/La₃NdO₆ Lu/La₃NdO₆In/La₃NdO₆ LaNd₃O₆ Tb/LaNd₃O₆ Dy/LaNd₃O₆ Ho/LaNd₃O₆ Er/LaNd₃O₆Tm/LaNd₃O₆ Yb/LaNd₃O₆ Lu/LaNd₃O₆ In/LaNd₃O₆ La_(1.5)Nd_(2.5)O₆Tb/La_(1.5)Nd_(2.5)O₆ Dy/La_(1.5)Nd_(2.5)O₆ Ho/La_(1.5)Nd_(2.5)O₆Er/La_(1.5)Nd_(2.5)O₆ Tm/La_(1.5)Nd_(2.5)O₆ Yb/La_(1.5)Nd_(2.5)O₆Lu/La_(1.5)Nd_(2.5)O₆ In/La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆Tb/La_(2.5)Nd_(1.5)O₆ Dy/La_(2.5)Nd_(1.5)O₆ Ho/La_(2.5)Nd_(1.5)O₆Er/La_(2.5)Nd_(1.5)O₆ Tm/La_(2.5)Nd_(1.5)O₆ Yb/La_(2.5)Nd_(1.5)O₆Lu/La_(2.5)Nd_(1.5)O₆ In/La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆Tb/La_(3.2)Nd_(0.8)O₆ Dy/La_(3.2)Nd_(0.8)O₆ Ho/La_(3.2)Nd_(0.8)O₆Er/La_(3.2)Nd_(0.8)O₆ Tm/La_(3.2)Nd_(0.8)O₆ Yb/La_(3.2)Nd_(0.8)O₆Lu/La_(3.2)Nd_(0.8)O₆ In/La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆Tb/La_(3.5)Nd_(0.5)O₆ Dy/La_(3.5)Nd_(0.5)O₆ Ho/La_(3.5)Nd_(0.5)O₆Er/La_(3.5)Nd_(0.5)O₆ Tm/La_(3.5)Nd_(0.5)O₆ Yb/La_(3.5)Nd_(0.5)O₆Lu/La_(3.5)Nd_(0.5)O₆ In/La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆Tb/La_(3.8)Nd_(0.2)O₆ Dy/La_(3.8)Nd_(0.2)O₆ Ho/La_(3.8)Nd_(0.2)O₆Er/La_(3.8)Nd_(0.2)O₆ Tm/La_(3.8)Nd_(0.2)O₆ Yb/La_(3.8)Nd_(0.2)O₆Lu/La_(3.8)Nd_(0.2)O₆ In/La_(3.8)Nd_(0.2)O₆ Y—La Tb/Y—La Dy/Y—La Ho/Y—LaEr/Y—La Tm/Y—La Yb/Y—La Lu/Y—La In/Y—La Zr—La Tb/Zr—La Dy/Zr—La Ho/Zr—LaEr/Zr—La Tm/Zr—La Yb/Zr—La Lu/Zr—La In/Zr—La Pr—La Tb/Pr—La Dy/Pr—LaHo/Pr—La Er/Pr—La Tm/Pr—La Yb/Pr—La Lu/Pr—La In/Pr—La Ce—La Tb/Ce—LaDy/Ce—La Ho/Ce—La Er/Ce—La Tm/Ce—La Yb/Ce—La Lu/Ce—La In/Ce—La

TABLE 5 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Y Sc AlCu Ga Hf Fe Cr Li₂O Y/Li₂O Sc/Li₂O Al/Li₂O Cu/Li₂O Ga/Li₂O Hf/Li₂OFe/Li₂O Cr/Li₂O Na₂O Y/Na₂O Sc/Na₂O Al/Na₂O Cu/Na₂O Ga/Na₂O Hf/Na₂OFe/Na₂O Cr/Na₂O K₂O Y/K₂O Sc/K₂O Al/K₂O Cu/K₂O Ga/K₂O Hf/K₂O Fe/K₂OCr/K₂O Rb₂O Y/Rb₂O Sc/Rb₂O Al/Rb₂O Cu/Rb₂O Ga/Rb₂O Hf/Rb₂O Fe/Rb₂OCr/Rb₂O Cs₂O Y/Cs₂O Sc/Cs₂O Al/Cs₂O Cu/Cs₂O Ga/Cs₂O Hf/Cs₂O Fe/Cs₂OCr/Cs₂O BeO Y/BeO Sc/BeO Al/BeO Cu/BeO Ga/BeO Hf/BeO Fe/BeO Cr/BeO MgOY/MgO Sc/MgO Al/MgO Cu/MgO Ga/MgO Hf/MgO Fe/MgO Cr/MgO CaO Y/CaO Sc/CaOAl/CaO Cu/CaO Ga/CaO Hf/CaO Fe/CaO Cr/CaO SrO Y/SrO Sc/SrO Al/SrO Cu/SrOGa/SrO Hf/SrO Fe/SrO Cr/SrO BaO Y/BaO Sc/BaO Al/BaO Cu/BaO Ga/BaO Hf/BaOFe/BaO Cr/BaO Sc₂O₃ Y/Sc₂O₃ Sc/Sc₂O₃ Al/Sc₂O₃ Cu/Sc₂O₃ Ga/Sc₂O₃ Hf/Sc₂O₃Fe/Sc₂O₃ Cr/Sc₂O₃ Y₂O₃ Y/Y₂O₃ Sc/Y₂O₃ Al/Y₂O₃ Cu/Y₂O₃ Ga/Y₂O₃ Hf/Y₂O₃Fe/Y₂O₃ Cr/Y₂O₃ La₂O₃ Y/La₂O₃ Sc/La₂O₃ Al/La₂O₃ Cu/La₂O₃ Ga/La₂O₃Hf/La₂O₃ Fe/La₂O₃ Cr/La₂O₃ CeO₂ Y/CeO₂ Sc/CeO₂ Al/CeO₂ Cu/CeO₂ Ga/CeO₂Hf/CeO₂ Fe/CeO₂ Cr/CeO₂ Ce₂O₃ Y/Ce₂O₃ Sc/Ce₂O₃ Al/Ce₂O₃ Cu/Ce₂O₃Ga/Ce₂O₃ Hf/Ce₂O₃ Fe/Ce₂O₃ Cr/Ce₂O₃ Pr₂O₃ Y/Pr₂O₃ Sc/Pr₂O₃ Al/Pr₂O₃Cu/Pr₂O₃ Ga/Pr₂O₃ Hf/Pr₂O₃ Fe/Pr₂O₃ Cr/Pr₂O₃ Nd₂O₃ Y/Nd₂O₃ Sc/Nd₂O₃Al/Nd₂O₃ Cu/Nd₂O₃ Ga/Nd₂O₃ Hf/Nd₂O₃ Fe/Nd₂O₃ Cr/Nd₂O₃ Sm₂O₃ Y/Sm₂O₃Sc/Sm₂O₃ Al/Sm₂O₃ Cu/Sm₂O₃ Ga/Sm₂O₃ Hf/Sm₂O₃ Fe/Sm₂O₃ Cr/Sm₂O₃ Eu₂O₃Y/Eu₂O₃ Sc/Eu₂O₃ Al/Eu₂O₃ Cu/Eu₂O₃ Ga/Eu₂O₃ Hf/Eu₂O₃ Fe/Eu₂O₃ Cr/Eu₂O₃Gd₂O₃ Y/Gd₂O₃ Sc/Gd₂O₃ Al/Gd₂O₃ Cu/Gd₂O₃ Ga/Gd₂O₃ Hf/Gd₂O₃ Fe/Gd₂O₃Cr/Gd₂O₃ Tb₂O₃ Y/Tb₂O₃ Sc/Tb₂O₃ Al/Tb₂O₃ Cu/Tb₂O₃ Ga/Tb₂O₃ Hf/Tb₂O₃Fe/Tb₂O₃ Cr/Tb₂O₃ TbO₂ Y/TbO₂ Sc/TbO₂ Al/TbO₂ Cu/TbO₂ Ga/TbO₂ Hf/TbO₂Fe/TbO₂ Cr/TbO₂ Tb₆O₁₁ Y/Tb₆O₁₁ Sc/Tb₆O₁₁ Al/Tb₆O₁₁ Cu/Tb₆O₁₁ Ga/Tb₆O₁₁Hf/Tb₆O₁₁ Fe/Tb₆O₁₁ Cr/Tb₆O₁₁ Dy₂O₃ Y/Dy₂O₃ Sc/Dy₂O₃ Al/Dy₂O₃ Cu/DyO₃Ga/Dy₂O₃ Hf/DyO₃ Fe/Dy₂O₃ Cr/Dy₂O₃ Ho₂O₃ Y/Ho₂O₃ Sc/Ho₂O₃ Al/Ho₂O₃Cu/Ho₂O₃ Ga/Ho₂O₃ Hf/Ho₂O₃ Fe/Ho₂O₃ Cr/Ho₂O₃ Er₂O₃ Y/Er₂O₃ Sc/Er₂O₃Al/Er₂O₃ Cu/Er₂O₃ Ga/Er₂O₃ Hf/Er₂O₃ Fe/Er₂O₃ Cr/Er₂O₃ Tm₂O₃ Y/Tm₂O₃Sc/Tm₂O₃ Al/Tm₂O₃ Cu/Tm₂O₃ Ga/Tm₂O₃ Hf/Tm₂O₃ Fe/Tm₂O₃ Cr/Tm₂O₃ Yb₂O₃Y/Yb₂O₃ Sc/Yb₂O₃ Al/Yb₂O₃ Cu/Yb₂O₃ Ga/Yb₂O₃ Hf/Yb₂O₃ Fe/Yb₂O₃ Cr/Yb₂O₃Lu₂O₃ Y/Lu₂O₃ Sc/Lu₂O₃ Al/Lu₂O₃ Cu/Lu₂O₃ Ga/Lu₂O₃ Hf/Lu₂O₃ Fe/Lu₂O₃Cr/Lu₂O₃ Ac₂O₃ Y/Ac₂O₃ Sc/Ac₂O₃ Al/Ac₂O₃ Cu/Ac₂O₃ Ga/Ac₂O₃ Hf/Ac₂O₃Fe/Ac₂O₃ Cr/Ac₂O₃ Th₂O₃ Y/Th₂O₃ Sc/Th₂O₃ Al/Th₂O₃ Cu/Th₂O₃ Ga/Th₂O₃Hf/Th₂O₃ Fe/Th₂O₃ Cr/Th₂O₃ ThO₂ Y/ThO₂ Sc/ThO₂ Al/ThO₂ Cu/ThO₂ Ga/ThO₂Hf/ThO₂ Fe/ThO₂ Cr/ThO₂ Pa₂O₃ Y/Pa₂O₃ Sc/Pa₂O₃ Al/Pa₂O₃ Cu/Pa₂O₃Ga/Pa₂O₃ Hf/Pa₂O₃ Fe/Pa₂O₃ Cr/Pa₂O₃ PaO₂ Y/PaO₂ Sc/PaO₂ Al/PaO₂ Cu/PaO₂Ga/PaO₂ Hf/PaO₂ Fe/PaO₂ Cr/PaO₂ TiO₂ Y/TiO₂ Sc/TiO₂ Al/TiO₂ Cu/TiO₂Ga/TiO₂ Hf/TiO₂ Fe/TiO₂ Cr/TiO₂ TiO Y/TiO Sc/TiO Al/TiO Cu/TiO Ga/TiOHf/TiO Fe/TiO Cr/TiO Ti₂O₃ Y/Ti₂O₃ Sc/Ti₂O₃ Al/Ti₂O₃ Cu/Ti₂O₃ Ga/Ti₂O₃Hf/Ti₂O₃ Fe/Ti₂O₃ Cr/Ti₂O₃ Ti₃O Y/Ti₃O Sc/Ti₃O Al/Ti₃O Cu/Ti₃O Ga/Ti₃OHf/Ti₃O Fe/Ti₃O Cr/Ti₃O Ti₂O Y/Ti₂O Sc/Ti₂O Al/Ti₂O Cu/Ti₂O Ga/Ti₂OHf/Ti₂O Fe/Ti₂O Cr/Ti₂O Ti₃O₅ Y/Ti₃O₅ Sc/Ti₃O₅ Al/Ti₃O₅ Cu/Ti₃O₅Ga/Ti₃O₅ Hf/Ti₃O₅ Fe/Ti₃O₅ Cr/Ti₃O₅ Ti₄O₇ Y/Ti₄O₇ Sc/Ti₄O₇ Al/Ti₄O₇Cu/Ti₄O₇ Ga/Ti₄O₇ Hf/Ti₄O₇ Fe/Ti₄O₇ Cr/Ti₄O₇ ZrO₂ Y/ZrO₂ Sc/ZrO₂ Al/ZrO₂Cu/ZrO₂ Ga/ZrO₂ Hf/ZrO₂ Fe/ZrO₂ Cr/ZrO₂ HfO₂ Y/HfO₂ Sc/HfO₂ Al/HfO₂Cu/HfO₂ Ga/HfO₂ Hf/HfO₂ Fe/HfO₂ Cr/HfO₂ VO Y/VO Sc/VO Al/VO Cu/VO Ga/VOHf/VO Fe/VO Cr/VO V₂O₃ Y/V₂O₃ Sc/V₂O₃ Al/V₂O₃ Cu/V₂O₃ Ga/V₂O₃ Hf/V₂O₃Fe/V₂O₃ Cr/V₂O₃ VO₂ Y/VO₂ Sc/VO₂ Al/VO₂ Cu/VO₂ Ga/VO₂ Hf/VO₂ Fe/VO₂Cr/VO₂ V₂O₅ Y/V₂O₅ Sc/V₂O₅ Al/V₂O₅ Cu/V₂O₅ Ga/V₂O₅ Hf/V₂O₅ Fe/V₂O₅Cr/V₂O₅ V₃O₇ Y/V₃O₇ Sc/V₃O₇ Al/V₃O₇ Cu/V₃O₇ Ga/V₃O₇ Hf/V₃O₇ Fe/V₃O₇Cr/V₃O₇ V₄O₉ Y/V₄O₉ Sc/V₄O₉ Al/V₄O₉ Cu/V₄O₉ Ga/V₄O₉ Hf/V₄O₉ Fe/V₄O₉Cr/V₄O₉ V₆O₁₃ Y/V₆O₁₃ Sc/V₆O₁₃ Al/V₆O₁₃ Cu/V₆O₁₃ Ga/V₆O₁₃ Hf/V₆O₁₃Fe/V₆O₁₃ Cr/V₆O₁₃ NbO Y/NbO Sc/NbO Al/NbO Cu/NbO Ga/NbO Hf/NbO Fe/NbOCr/NbO NbO₂ Y/NbO₂ Sc/NbO₂ Al/NbO₂ Cu/NbO₂ Ga/NbO₂ Hf/NbO₂ Fe/NbO₂Cr/NbO₂ Nb₂O₅ Y/Nb₂O₅ Sc/Nb₂O₅ Al/Nb₂O₅ Cu/Nb₂O₅ Ga/Nb₂O₅ Hf/Nb₂O₅Fe/Nb₂O₅ Cr/Nb₂O₅ Nb₈O₁₉ Y/Nb₈O₁₉ Sc/Nb₈O₁₉ Al/Nb₈O₁₉ Cu/Nb₈O₁₉Ga/Nb₈O₁₉ Hf/Nb₈O₁₉ Fe/Nb₈O₁₉ Cr/Nb₈O₁₉ Nb₁₆O₃₈ Y/Nb₁₆O₃₈ Sc/Nb₁₆O₃₈Al/Nb₁₆O₃₈ Cu/Nb₁₆O₃₈ Ga/Nb₁₆O₃₈ Hf/Nb₁₆O₃₈ Fe/Nb₁₆O₃₈ Cr/Nb₁₆O₃₈Nb₁₂O₂₉ Y/Nb₁₂O₂₉ Sc/Nb₁₂O₂₉ Al/Nb₁₂O₂₉ Cu/Nb₁₂O₂₉ Ga/Nb₁₂O₂₉ Hf/Nb₁₂O₂₉Fe/Nb₁₂O₂₉ Cr/Nb₁₂O₂₉ Nb₄₇O₁₁₆ Y/Nb₄₇O₁₁₆ Sc/Nb₄₇O₁₁₆ Al/Nb₄₇O₁₁₆Cu/Nb₄₇O₁₁₆ Ga/Nb₄₇O₁₁₆ Hf/Nb₄₇O₁₁₆ Fe/Nb₄₇O₁₁₆ Cr/Nb₄₇O₁₁₆ Ta₂O₅Y/Ta₂O₅ Sc/Ta₂O₅ Al/Ta₂O₅ Cu/Ta₂O₅ Ga/Ta₂O₅ Hf/Ta₂O₅ Fe/Ta₂O₅ Cr/Ta₂O₅CrO Y/CrO Sc/CrO Al/CrO Cu/CrO Ga/CrO Hf/CrO Fe/CrO Cr/CrO Cr₂O₃ Y/Cr₂O₃Sc/Cr₂O₃ Al/Cr₂O₃ Cu/Cr₂O₃ Ga/Cr₂O₃ Hf/Cr₂O₃ Fe/Cr₂O₃ Cr/Cr₂O₃ CrO₂Y/CrO₂ Sc/CrO₂ Al/CrO₂ Cu/CrO₂ Ga/CrO₂ Hf/CrO₂ Fe/CrO₂ Cr/CrO₂ CrO₃Y/CrO₃ Sc/CrO₃ Al/CrO₃ Cu/CrO₃ Ga/CrO₃ Hf/CrO₃ Fe/CrO₃ Cr/CrO₃ Cr₈O₂₁Y/Cr₈O₂₁ Sc/Cr₈O₂₁ Al/Cr₈O₂₁ Cu/Cr₈O₂₁ Ga/Cr₈O₂₁ Hf/Cr₈O₂₁ Fe/Cr₈O₂₁Cr/Cr₈O₂₁ MoO₂ Y/MoO₂ Sc/MoO₂ Al/MoO₂ Cu/MoO₂ Ga/MoO₂ Hf/MoO₂ Fe/MoO₂Cr/MoO₂ MoO₃ Y/MoO₃ Sc/MoO₃ Al/MoO₃ Cu/MoO₃ Ga/MoO₃ Hf/MoO₃ Fe/MoO₃Cr/MoO₃ W₂O₃ Y/W₂O₃ Sc/W₂O₃ Al/W₂O₃ Cu/W₂O₃ Ga/W₂O₃ Hf/W₂O₃ Fe/W₂O₃Cr/W₂O₃ WoO₂ Y/WoO₂ Sc/WoO₂ Al/WoO₂ Cu/WoO₂ Ga/WoO₂ Hf/WoO₂ Fe/WoO₂Cr/WoO₂ WoO₃ Y/WoO₃ Sc/WoO₃ Al/WoO₃ Cu/WoO₃ Ga/WoO₃ Hf/WoO₃ Fe/WoO₃Cr/WoO₃ MnO Y/MnO Sc/MnO Al/MnO Cu/MnO Ga/MnO Hf/MnO Fe/MnO Cr/MnOMn/Mg/O Y/Mn/Mg/O Sc/Mn/Mg/O Al/Mn/Mg/O Cu/Mn/Mg/O Ga/Mn/Mg/O Hf/Mn/Mg/OFe/Mn/Mg/O Cr/Mn/Mg/O Mn₃O₄ Y/Mn₃O₄ Sc/Mn₃O₄ Al/Mn₃O₄ Cu/Mn₃O₄ Ga/Mn₃O₄Hf/Mn₃O₄ Fe/Mn₃O₄ Cr/Mn₃O₄ Mn₂O₃ Y/Mn₂O₃ Sc/Mn₂O₃ Al/Mn₂O₃ Cu/Mn₂O₃Ga/Mn₂O₃ Hf/Mn₂O₃ Fe/Mn₂O₃ Cr/Mn₂O₃ MnO₂ Y/MnO₂ Sc/MnO₂ Al/MnO₂ Cu/MnO₂Ga/MnO₂ Hf/MnO₂ Fe/MnO₂ Cr/MnO₂ Mn₂O₇ Y/Mn₂O₇ Sc/Mn₂O₇ Al/Mn₂O₇ Cu/Mn₂O₇Ga/Mn₂O₇ Hf/Mn₂O₇ Fe/Mn₂O₇ Cr/Mn₂O₇ ReO₂ Y/ReO₂ Sc/ReO₂ Al/ReO₂ Cu/ReO₂Ga/ReO₂ Hf/ReO₂ Fe/ReO₂ Cr/ReO₂ ReO₃ Y/ReO₃ Sc/ReO₃ Al/ReO₃ Cu/ReO₃Ga/ReO₃ Hf/ReO₃ Fe/ReO₃ Cr/ReO₃ Re₂O₇ Y/Re₂O₇ Sc/Re₂O₇ Al/Re₂O₇ Cu/Re₂O₇Ga/Re₂O₇ Hf/Re₂O₇ Fe/Re₂O₇ Cr/Re₂O₇ Mg₃Mn₃—B₂O₁₀ Y/Mg₃Mn₃—B₂O₁₀Sc/Mg₃Mn₃—B₂O₁₀ Al/Mg₃Mn₃—B₂O₁₀ Cu/Mg₃Mn₃—B₂O₁₀ Ga/Mg₃Mn₃—B₂O₁₀Hf/Mg₃Mn₃—B₂O₁₀ Fe/Mg₃Mn₃—B₂O₁₀ Cr/Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Y/Mg₃(BO₃)₂Sc/Mg₃(BO₃)₂ Al/Mg₃(BO₃)₂ Cu/Mg₃(BO₃)₂ Ga/Mg₃(BO₃)₂ Hf/Mg₃(BO₃)₂Fe/Mg₃(BO₃)₂ Cr/Mg₃(BO₃)₂ NaWO₄ Y/NaWO₄ Sc/NaWO₄ Al/NaWO₄ Cu/NaWO₄Ga/NaWO₄ Hf/NaWO₄ Fe/NaWO₄ Cr/NaWO₄ Mg₆MnO₈ Y/Mg₆MnO₈ Sc/Mg₆MnO₈Al/Mg₆MnO₈ Cu/Mg₆MnO₈ Ga/Mg₆MnO₈ Hf/Mg₆MnO₈ Fe/Mg₆MnO₈ Cr/Mg₆MnO₈ Mn₂O₄Y/Mn₂O₄ Sc/Mn₂O₄ Al/Mn₂O₄ Cu/Mn₂O₄ Ga/Mn₂O₄ Hf/Mn₂O₄ Fe/Mn₂O₄ Cr/Mn₂O₄(Li,Mg)₆MnO₈ Y/(Li,Mg)₆MnO₈ Sc/(Li,Mg)₆MnO₈ Al/(Li,Mg)₆MnO₈Cu/(Li,Mg)₆MnO₈ Ga/(Li,Mg)₆MnO₈ Hf/(Li,Mg)₆MnO₈ Fe/(Li,Mg)₆MnO₈Cr/(Li,Mg)₆MnO₈ Na₄P₂O₇ Y/Na₄P₂O₇ Sc/Na₄P₂O₇ Al/Na₄P₂O₇ Cu/Na₄P₂O₇Ga/Na₄P₂O₇ Hf/Na₄P₂O₇ Fe/Na₄P₂O₇ Cr/Na₄P₂O₇ Mo₂O₈ Y/Mo₂O₈ Sc/Mo₂O₈Al/Mo₂O₈ Cu/Mo₂O₈ Ga/Mo₂O₈ Hf/Mo₂O₈ Fe/Mo₂O₈ Cr/Mo₂O₈ Mn₃O₄/WO₄Y/Mn₃O₄/WO₄ Sc/Mn₃O₄/WO₄ Al/Mn₃O₄/WO₄ Cu/Mn₃O₄/WO₄ Ga/Mn₃O₄/WO₄Hf/Mn₃O₄/WO₄ Fe/Mn₃O₄/WO₄ Cr/Mn₃O₄/WO₄ Na₂WO₄ Y/Na₂WO₄ Sc/Na₂WO₄Al/Na₂WO₄ Cu/Na₂WO₄ Ga/Na₂WO₄ Hf/Na₂WO₄ Fe/Na₂WO₄ Cr/Na₂WO₄ Zr₂Mo₂O₈Y/Zr₂Mo₂O₈ Sc/Zr₂Mo₂O₈ Al/Zr₂Mo₂O₈ Cu/Zr₂Mo₂O₈ Ga/Zr₂Mo₂O₈ Hf/Zr₂Mo₂O₈Fe/Zr₂Mo₂O₈ Cr/Zr₂Mo₂O₈ NaMnO₄—/MgO Y/NaMnO₄—/MgO Sc/NaMnO₄—/MgOAl/NaMnO₄—/MgO Cu/NaMnO₄—/MgO Ga/NaMnO₄—/MgO Hf/NaMnO₄—/MgOFe/NaMnO₄—/MgO Cr/NaMnO₄—/MgO Na₁₀Mn—W₅O₁₇ Y/Na₁₀Mn—W₅O₁₇Sc/Na₁₀Mn—W₅O₁₇ Al/Na₁₀Mn—W₅O₁₇ Cu/Na₁₀Mn—W₅O₁₇ Ga/Na₁₀Mn—W₅O₁₇Hf/Na₁₀Mn—W₅O₁₇ Fe/Na₁₀Mn—W₅O₁₇ Cr/Na₁₀Mn—W₅O₁₇ La₃NdO₆ Y/La₃NdO₆Sc/La₃NdO₆ Al/La₃NdO₆ Cu/La₃NdO₆ Ga/La₃NdO₆ Hf/La₃NdO₆ Fe/La₃NdO₆Cr/La₃NdO₆ LaNd₃O₆ Y/LaNd₃O₆ Sc/LaNd₃O₆ Al/LaNd₃O₆ Cu/LaNd₃O₆ Ga/LaNd₃O₆Hf/LaNd₃O₆ Fe/LaNd₃O₆ Cr/LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ Y/La_(1.5)Nd_(2.5)O₆Sc/La_(1.5)Nd_(2.5)O₆ Al/La_(1.5)Nd_(2.5)O₆ Cu/La_(1.5)Nd_(2.5)O₆Ga/La_(1.5)Nd_(2.5)O₆ Hf/La_(1.5)Nd_(2.5)O₆ Fe/La_(1.5)Nd_(2.5)O₆Cr/La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ Y/La_(2.5)Nd_(1.5)O₆Sc/La_(2.5)Nd_(1.5)O₆ Al/La_(2.5)Nd_(1.5)O₆ Cu/La_(2.5)Nd_(1.5)O₆Ga/La_(2.5)Nd_(1.5)O₆ Hf/La_(2.5)Nd_(1.5)O₆ Fe/La_(2.5)Nd_(1.5)O₆Cr/La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ Y/La_(3.2)Nd_(0.8)O₆Sc/La_(3.2)Nd_(0.8)O₆ Al/La_(3.2)Nd_(0.8)O₆ Cu/La_(3.2)Nd_(0.8)O₆Ga/La_(3.2)Nd_(0.8)O₆ Hf/La_(3.2)Nd_(0.8)O₆ Fe/La_(3.2)Nd_(0.8)O₆Cr/La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Y/La_(3.5)Nd_(0.5)O₆Sc/La_(3.5)Nd_(0.5)O₆ Al/La_(3.5)Nd_(0.5)O₆ Cu/La_(3.5)Nd_(0.5)O₆Ga/La_(3.5)Nd_(0.5)O₆ Hf/La_(3.5)Nd_(0.5)O₆ Fe/La_(3.5)Nd_(0.5)O₆Cr/La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆ Y/La_(3.8)Nd_(0.2)O₆Sc/La_(3.8)Nd_(0.2)O₆ Al/La_(3.8)Nd_(0.2)O₆ Cu/La_(3.8)Nd_(0.2)O₆Ga/La_(3.8)Nd_(0.2)O₆ Hf/La_(3.8)Nd_(0.2)O₆ Fe/La_(3.8)Nd_(0.2)O₆Cr/La_(3.8)Nd_(0.2)O₆ Y—La Y/Y—La Sc/Y—La Al/Y—La Cu/Y—La Ga/Y—LaHf/Y—La Fe/Y—La Cr/Y—La Zr—La Y/Zr—La Sc/Zr—La Al/Zr—La Cu/Zr—LaGa/Zr—La Hf/Zr—La Fe/Zr—La Cr/Zr—La Pr—La Y/Pr—La Sc/Pr—La Al/Pr—LaCu/Pr—La Ga/Pr—La Hf/Pr—La Fe/Pr—La Cr/Pr—La Ce—La Y/Ce—La Sc/Ce—LaAl/Ce—La Cu/Ce—La Ga/Ce—La Hf/Ce—La Fe/Ce—La Cr/Ce—La

TABLE 6 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Ru Zr TaRh Li₂O Ru/Li₂O Zr/Li₂O Ta/Li₂O Rh/Li₂O Na₂O Ru/Na₂O Zr/Na₂O Ta/Na₂ORh/Na₂O K₂O Ru/K₂O Zr/K₂O Ta/K₂O Rh/K₂O Rb₂O Ru/Rb₂O Zr/Rb₂O Ta/Rb₂ORh/Rb₂O Cs₂O Ru/Cs₂O Zr/Cs₂O Ta/Cs₂O Rh/Cs₂O BeO Ru/BeO Zr/BeO Ta/BeORh/BeO MgO Ru/MgO Zr/MgO Ta/MgO Rh/MgO CaO Ru/CaO Zr/CaO Ta/CaO Rh/CaOSrO Ru/SrO Zr/SrO Ta/SrO Rh/SrO BaO Ru/BaO Zr/BaO Ta/BaO Rh/BaO Sc₂O₃Ru/Sc₂O₃ Zr/Sc₂O₃ Ta/Sc₂O₃ Rh/Sc₂O₃ Y₂O₃ Ru/Y₂O₃ Zr/Y₂O₃ Ta/Y₂O₃ Rh/Y₂O₃La₂O₃ Ru/La₂O₃ Zr/La₂O₃ Ta/La₂O₃ Rh/La₂O₃ CeO₂ Ru/CeO₂ Zr/CeO₂ Ta/CeO₂Rh/CeO₂ Ce₂O₃ Ru/Ce₂O₃ Zr/Ce₂O₃ Ta/Ce₂O₃ Rh/Ce₂O₃ Pr₂O₃ Ru/Pr₂O₃Zr/Pr₂O₃ Ta/Pr₂O₃ Rh/Pr₂O₃ Nd₂O₃ Ru/Nd₂O₃ Zr/Nd₂O₃ Ta/Nd₂O₃ Rh/Nd₂O₃Sm₂O₃ Ru/Sm₂O₃ Zr/Sm₂O₃ Ta/Sm₂O₃ Rh/Sm₂O₃ Eu₂O₃ Ru/Eu₂O₃ Zr/Eu₂O₃Ta/Eu₂O₃ Rh/Eu₂O₃ Gd₂O₃ Ru/Gd₂O₃ Zr/Gd₂O₃ Ta/Gd₂O₃ Rh/Gd₂O₃ Tb₂O₃Ru/Tb₂O₃ Zr/Tb₂O₃ Ta/Tb₂O₃ Rh/Tb₂O₃ TbO₂ Ru/TbO₂ Zr/TbO₂ Ta/TbO₂ Rh/TbO₂Tb₆O₁₁ Ru/Tb₆O₁₁ Zr/Tb₆O₁₁ Ta/Tb₆O₁₁ Rh/Tb₆O₁₁ Dy₂O₃ Ru/Dy₂O₃ Zr/Dy₂O₃Ta/Dy₂O₃ Rh/Dy₂O₃ Ho₂O₃ Ru/Ho₂O₃ Zr/Ho₂O₃ Ta/Ho₂O₃ Rh/Ho₂O₃ Er₂O₃Ru/Er₂O₃ Zr/Er₂O₃ Ta/Er₂O₃ Rh/Er₂O₃ Tm₂O₃ Ru/Tm₂O₃ Zr/Tm₂O₃ Ta/Tm₂O₃Rh/Tm₂O₃ Yb₂O₃ Ru/Yb₂O₃ Zr/Yb₂O₃ Ta/Yb₂O₃ Rh/Yb₂O₃ Lu₂O₃ Ru/Lu₂O₃Zr/Lu₂O₃ Ta/Lu₂O₃ Rh/Lu₂O₃ Ac₂O₃ Ru/Ac₂O₃ Zr/Ac₂O₃ Ta/Ac₂O₃ Rh/Ac₂O₃Th₂O₃ Ru/Th₂O₃ Zr/Th₂O₃ Ta/Th₂O₃ Rh/Th₂O₃ ThO₂ Ru/ThO₂ Zr/ThO₂ Ta/ThO₂Rh/ThO₂ Pa₂O₃ Ru/Pa₂O₃ Zr/Pa₂O₃ Ta/Pa₂O₃ Rh/Pa₂O₃ PaO₂ Ru/PaO₂ Zr/PaO₂Ta/PaO₂ Rh/PaO₂ TiO₂ Ru/TiO₂ Zr/TiO₂ Ta/TiO₂ Rh/TiO₂ TiO Ru/TiO Zr/TiOTa/TiO Rh/TiO Ti₂O₃ Ru/Ti₂O₃ Zr/Ti₂O₃ Ta/Ti₂O₃ Rh/Ti₂O₃ Ti₃O Ru/Ti₃OZr/Ti₃O Ta/Ti₃O Rh/Ti₃O Ti₂O Ru/Ti₂O Zr/Ti₂O Ta/Ti₂O Rh/Ti₂O Ti₃O₅Ru/Ti₃O₅ Zr/Ti₃O₅ Ta/Ti₃O₅ Rh/Ti₃O₅ Ti₄O₇ Ru/Ti₄O₇ Zr/Ti₄O₇ Ta/Ti₄O₇Rh/Ti₄O₇ ZrO₂ Ru/ZrO₂ Zr/ZrO₂ Ta/ZrO₂ Rh/ZrO₂ HfO₂ Ru/HfO₂ Zr/HfO₂Ta/HfO₂ Rh/HfO₂ VO Ru/VO Zr/VO Ta/VO Rh/VO V₂O₃ Ru/V₂O₃ Zr/V₂O₃ Ta/V₂O₃Rh/V₂O₃ VO₂ Ru/VO₂ Zr/VO₂ Ta/VO₂ Rh/VO₂ V₂O₅ Ru/V₂O₅ Zr/V₂O₅ Ta/V₂O₅Rh/V₂O₅ V₃O₇ Ru/V₃O₇ Zr/V₃O₇ Ta/V₃O₇ Rh/V₃O₇ V₄O₉ Ru/V₄O₉ Zr/V₄O₉Ta/V₄O₉ Rh/V₄O₉ V₆O₁₃ Ru/V₆O₁₃ Zr/V₆O₁₃ Ta/V₆O₁₃ Rh/V₆O₁₃ NbO Ru/NbOZr/NbO Ta/NbO Rh/NbO NbO₂ Ru/NbO₂ Zr/NbO₂ Ta/NbO₂ Rh/NbO₂ Nb₂O₅ Ru/Nb₂O₅Zr/Nb₂O₅ Ta/Nb₂O₅ Rh/Nb₂O₅ Nb₈O₁₉ Ru/Nb₈O₁₉ Zr/Nb₈O₁₉ Ta/Nb₈O₁₉Rh/Nb₈O₁₉ Nb₁₆O₃₈ Ru/Nb₁₆O₃₈ Zr/Nb₁₆O₃₈ Ta/Nb₁₆O₃₈ Rh/Nb₁₆O₃₈ Nb₁₂O₂₉Ru/Nb₁₂O₂₉ Zr/Nb₁₂O₂₉ Ta/Nb₁₂O₂₉ Rh/Nb₁₂O₂₉ Nb₄₇O₁₁₆ Ru/Nb₄₇O₁₁₆Zr/Nb₄₇O₁₁₆ Ta/Nb₄₇O₁₁₆ Rh/Nb₄₇O₁₁₆ Ta₂O₅ Ru/Ta₂O₅ Zr/Ta₂O₅ Ta/Ta₂O₅Rh/Ta₂O₅ CrO Ru/CrO Zr/CrO Ta/CrO Rh/CrO Cr₂O₃ Ru/Cr₂O₃ Zr/Cr₂O₃Ta/Cr₂O₃ Rh/Cr₂O₃ CrO₂ Ru/CrO₂ Zr/CrO₂ Ta/CrO₂ Rh/CrO₂ CrO₃ Ru/CrO₃Zr/CrO₃ Ta/CrO₃ Rh/CrO₃ Cr₈O₂₁ Ru/Cr₈O₂₁ Zr/Cr₈O₂₁ Ta/Cr₈O₂₁ Rh/Cr₈O₂₁MoO₂ Ru/MoO₂ Zr/MoO₂ Ta/MoO₂ Rh/MoO₂ MoO₃ Ru/MoO₃ Zr/MoO₃ Ta/MoO₃Rh/MoO₃ W₂O₃ Ru/W₂O₃ Zr/W₂O₃ Ta/W₂O₃ Rh/W₂O₃ WoO₂ Ru/WoO₂ Zr/WoO₂Ta/WoO₂ Rh/WoO₂ WoO₃ Ru/WoO₃ Zr/WoO₃ Ta/WoO₃ Rh/WoO₃ MnO Ru/MnO Zr/MnOTa/MnO Rh/MnO Mn/Mg/O Ru/Mn/Mg/O Zr/Mn/Mg/O Ta/Mn/Mg/O Rh/Mn/Mg/O Mn₃O₄Ru/Mn₃O₄ Zr/Mn₃O₄ Ta/Mn₃O₄ Rh/Mn₃O₄ Mn₂O₃ Ru/Mn₂O₃ Zr/Mn₂O₃ Ta/Mn₂O₃Rh/Mn₂O₃ MnO₂ Ru/MnO₂ Zr/MnO₂ Ta/MnO₂ Rh/MnO₂ Mn₂O₇ Ru/Mn₂O₇ Zr/Mn₂O₇Ta/Mn₂O₇ Rh/Mn₂O₇ ReO₂ Ru/ReO₂ Zr/ReO₂ Ta/ReO₂ Rh/ReO₂ ReO₃ Ru/ReO₃Zr/ReO₃ Ta/ReO₃ Rh/ReO₃ Re₂O₇ Ru/Re₂O₇ Zr/Re₂O₇ Ta/Re₂O₇ Rh/Re₂O₇Mg₃Mn₃—B₂O₁₀ Ru/Mg₃Mn₃—B₂O₁₀ Zr/Mg₃Mn₃—B₂O₁₀ Ta/Mg₃Mn₃—B₂O₁₀Rh/Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Ru/Mg₃(BO₃)₂ Zr/Mg₃(BO₃)₂ Ta/Mg₃(BO₃)₂Rh/Mg₃(BO₃)₂ NaWO₄ Ru/NaWO₄ Zr/NaWO₄ Ta/NaWO₄ Rh/NaWO₄ Mg₆MnO₈Ru/Mg₆MnO₈ Zr/Mg₆MnO₈ Ta/Mg₆MnO₈ Rh/Mg₆MnO₈ Mn₂O₄ Ru/Mn₂O₄ Zr/Mn₂O₄Ta/Mn₂O₄ Rh/Mn₂O₄ (Li,Mg)₆—MnO₈ Ru/(Li,Mg)₆—MnO₈ Zr/(Li,Mg)₆—MnO₈Ta/(Li,Mg)₆—MnO₈ Rh/(Li,Mg)₆—MnO₈ Na₄P₂O₇ Ru/Na₄P₂O₇ Zr/Na₄P₂O₇Ta/Na₄P₂O₇ Rh/Na₄P₂O₇ Mo₂O₈ Ru/Mo₂O₈ Zr/Mo₂O₈ Ta/Mo₂O₈ Rh/Mo₂O₈Mn₃O₄/WO₄ Ru/Mn₃O₄/WO₄ Zr/Mn₃O₄/WO₄ Ta/Mn₃O₄/WO₄ Rh/Mn₃O₄/WO₄ Na₂WO₄Ru/Na₂WO₄ Zr/Na₂WO₄ Ta/Na₂WO₄ Rh/Na₂WO₄ Zr₂Mo₂O₈ Ru/Zr₂Mo₂O₈ Zr/Zr₂Mo₂O₈Ta/Zr₂Mo₂O₈ Rh/Zr₂Mo₂O₈ NaMnO₄—/MgO Ru/NaMnO₄—/MgO Zr/NaMnO₄—/MgOTa/NaMnO₄—/MgO Rh/NaMnO₄—/MgO Na₁₀Mn—W₅O₁₇ Ru/Na₁₀Mn—W₅O₁₇Zr/Na₁₀Mn—W₅O₁₇ Ta/Na₁₀Mn—W₅O₁₇ Rh/Na₁₀Mn—W₅O₁₇ La₃NdO₆ Ru/La₃NdO₆Zr/La₃NdO₆ Ta/La₃NdO₆ Rh/La₃NdO₆ LaNd₃O₆ Ru/LaNd₃O₆ Zr/LaNd₃O₆Ta/LaNd₃O₆ Rh/LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ Ru/La_(1.5)Nd_(2.5)O₆Zr/La_(1.5)Nd_(2.5)O₆ Ta/La_(1.5)Nd_(2.5)O₆ Rh/La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ Ru/La_(2.5)Nd_(1.5)O₆ Zr/La_(2.5)Nd_(1.5)O₆Ta/La_(2.5)Nd_(1.5)O₆ Rh/La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆Ru/La_(3.2)Nd_(0.8)O₆ Zr/La_(3.2)Nd_(0.8)O₆ Ta/La_(3.2)Nd_(0.8)O₆Rh/La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ru/La_(3.5)Nd_(0.5)O₆Zr/La_(3.5)Nd_(0.5)O₆ Ta/La_(3.5)Nd_(0.5)O₆ Rh/La_(3.5)Nd_(0.5)O₆La_(3.8)Nd_(0.2)O₆ Ru/La_(3.8)Nd_(0.2)O₆ Zr/La_(3.8)Nd_(0.2)O₆Ta/La_(3.8)Nd_(0.2)O₆ Rh/La_(3.8)Nd_(0.2)O₆ Y—La Ru/Y—La Zr/Y—La Ta/Y—LaRh/Y—La Zr—La Ru/Zr—La Zr/Zr—La Ta/Zr—La Rh/Zr—La Pr—La Ru/Pr—LaZr/Pr—La Ta/Pr—La Rh/Pr—La Ce—La Ru/Ce—La Zr/Ce—La Ta/Ce—La Rh/Ce—LaNW\Dop Au Mo Ni Li₂O Au/Li₂O Mo/Li₂O Ni/Li₂O Na₂O Au/Na₂O Mo/Na₂ONi/Na₂O K₂O Au/K₂O Mo/K₂O Ni/K₂O Rb₂O Au/Rb₂O Mo/Rb₂O Ni/Rb₂O Cs₂OAu/Cs₂O Mo/Cs₂O Ni/Cs₂O BeO Au/BeO Mo/BeO Ni/BeO MgO Au/MgO Mo/MgONi/MgO CaO Au/CaO Mo/CaO Ni/CaO SrO Au/SrO Mo/SrO Ni/SrO BaO Au/BaOMo/BaO Ni/BaO Sc₂O₃ Au/Sc₂O₃ Mo/Sc₂O₃ Ni/Sc₂O₃ Y₂O₃ Au/Y₂O₃ Mo/Y₂O₃Ni/Y₂O₃ La₂O₃ Au/La₂O₃ Mo/La₂O₃ Ni/La₂O₃ CeO₂ Au/CeO₂ Mo/CeO₂ Ni/CeO₂Ce₂O₃ Au/Ce₂O₃ Mo/Ce₂O₃ Ni/Ce₂O₃ Pr₂O₃ Au/Pr₂O₃ Mo/Pr₂O₃ Ni/Pr₂O₃ Nd₂O₃Au/Nd₂O₃ Mo/Nd₂O₃ Ni/Nd₂O₃ Sm₂O₃ Au/Sm₂O₃ Mo/Sm₂O₃ Ni/Sm₂O₃ Eu₂O₃Au/Eu₂O₃ Mo/Eu₂O₃ Ni/Eu₂O₃ Gd₂O₃ Au/Gd₂O₃ Mo/Gd₂O₃ Ni/Gd₂O₃ Tb₂O₃Au/Tb₂O₃ Mo/Tb₂O₃ Ni/Tb₂O₃ TbO₂ Au/TbO₂ Mo/TbO₂ Ni/TbO₂ Tb₆O₁₁ Au/Tb₆O₁₁Mo/Tb₆O₁₁ Ni/Tb₆O₁₁ Dy₂O₃ Au/Dy₂O₃ Mo/Dy₂O₃ Ni/Dy₂O₃ Ho₂O₃ Au/Ho₂O₃Mo/Ho₂O₃ Ni/Ho₂O₃ Er₂O₃ Au/Er₂O₃ Mo/Er₂O₃ Ni/Er₂O₃ Tm₂O₃ Au/Tm₂O₃Mo/Tm₂O₃ Ni/Tm₂O₃ Yb₂O₃ Au/Yb₂O₃ Mo/Yb₂O₃ Ni/Yb₂O₃ Lu₂O₃ Au/Lu₂O₃Mo/Lu₂O₃ Ni/Lu₂O₃ Ac₂O₃ Au/Ac₂O₃ Mo/Ac₂O₃ Ni/Ac₂O₃ Th₂O₃ Au/Th₂O₃Mo/Th₂O₃ Ni/Th₂O₃ ThO₂ Au/ThO₂ Mo/ThO₂ Ni/ThO₂ Pa₂O₃ Au/Pa₂O₃ Mo/Pa₂O₃Ni/Pa₂O₃ PaO₂ Au/PaO₂ Mo/PaO₂ Ni/PaO₂ TiO₂ Au/TiO₂ Mo/TiO₂ Ni/TiO₂ TiOAu/TiO Mo/TiO Ni/TiO Ti₂O₃ Au/Ti₂O₃ Mo/Ti₂O₃ Ni/Ti₂O₃ Ti₃O Au/Ti₃OMo/Ti₃O Ni/Ti₃O Ti₂O Au/Ti₂O Mo/Ti₂O Ni/Ti₂O Ti₃O₅ Au/Ti₃O₅ Mo/Ti₃O₅Ni/Ti₃O₅ Ti₄O₇ Au/Ti₄O₇ Mo/Ti₄O₇ Ni/Ti₄O₇ ZrO₂ Au/ZrO₂ Mo/ZrO₂ Ni/ZrO₂HfO₂ Au/HfO₂ Mo/HfO₂ Ni/HfO₂ VO Au/VO Mo/VO Ni/VO V₂O₃ Au/V₂O₃ Mo/V₂O₃Ni/V₂O₃ VO₂ Au/VO₂ Mo/VO₂ Ni/VO₂ V₂O₅ Au/V₂O₅ Mo/V₂O₅ Ni/V₂O₅ V₃O₇Au/V₃O₇ Mo/V₃O₇ Ni/V₃O₇ V₄O₉ Au/V₄O₉ Mo/V₄O₉ Ni/V₄O₉ V₆O₁₃ Au/V₆O₁₃Mo/V₆O₁₃ Ni/V₆O₁₃ NbO Au/NbO Mo/NbO Ni/NbO NbO₂ Au/NbO₂ Mo/NbO₂ Ni/NbO₂Nb₂O₅ Au/Nb₂O₅ Mo/Nb₂O₅ Ni/Nb₂O₅ Nb₈O₁₉ Au/Nb₈O₁₉ Mo/Nb₈O₁₉ Ni/Nb₈O₁₉Nb₁₆O₃₈ Au/Nb₁₆O₃₈ Mo/Nb₁₆O₃₈ Ni/Nb₁₆O₃₈ Nb₁₂O₂₉ Au/Nb₁₂O₂₉ Mo/Nb₁₂O₂₉Ni/Nb₁₂O₂₉ Nb₄₇O₁₁₆ Au/Nb₄₇O₁₁₆ Mo/Nb₄₇O₁₁₆ Ni/Nb₄₇O₁₁₆ Ta₂O₅ Au/Ta₂O₅Mo/Ta₂O₅ Ni/Ta₂O₅ CrO Au/CrO Mo/CrO Ni/CrO Cr₂O₃ Au/Cr₂O₃ Mo/Cr₂O₃Ni/Cr₂O₃ CrO₂ Au/CrO₂ Mo/CrO₂ Ni/CrO₂ CrO₃ Au/CrO₃ Mo/CrO₃ Ni/CrO₃Cr₈O₂₁ Au/Cr₈O₂₁ Mo/Cr₈O₂₁ Ni/Cr₈O₂₁ MoO₂ Au/MoO₂ Mo/MoO₂ Ni/MoO₂ MoO₃Au/MoO₃ Mo/MoO₃ Ni/MoO₃ W₂O₃ Au/W₂O₃ Mo/W₂O₃ Ni/W₂O₃ WoO₂ Au/WoO₂Mo/WoO₂ Ni/WoO₂ WoO₃ Au/WoO₃ Mo/WoO₃ Ni/WoO₃ MnO Au/MnO Mo/MnO Ni/MnOMn/Mg/O Au/Mn/Mg/O Mo/Mn/Mg/O Ni/Mn/Mg/O Mn₃O₄ Au/Mn₃O₄ Mo/Mn₃O₄Ni/Mn₃O₄ Mn₂O₃ Au/Mn₂O₃ Mo/Mn₂O₃ Ni/Mn₂O₃ MnO₂ Au/MnO₂ Mo/MnO₂ Ni/MnO₂Mn₂O₇ Au/Mn₂O₇ Mo/Mn₂O₇ Ni/Mn₂O₇ ReO₂ Au/ReO₂ Mo/ReO₂ Ni/ReO₂ ReO₃Au/ReO₃ Mo/ReO₃ Ni/ReO₃ Re₂O₇ Au/Re₂O₇ Mo/Re₂O₇ Ni/Re₂O₇ Mg₃Mn₃—B₂O₁₀Au/Mg₃Mn₃—B₂O₁₀ Mo/Mg₃Mn₃—B₂O₁₀ Ni/Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Au/Mg₃(BO₃)₂Mo/Mg₃(BO₃)₂ Ni/Mg₃(BO₃)₂ NaWO₄ Au/NaWO₄ Mo/NaWO₄ Ni/NaWO₄ Mg₆MnO₈Au/Mg₆MnO₈ Mo/Mg₆MnO₈ Ni/Mg₆MnO₈ Mn₂O₄ Au/Mn₂O₄ Mo/Mn₂O₄ Ni/Mn₂O₄(Li,Mg)₆—MnO₈ Au/(Li,Mg)₆—MnO₈ Mo/(Li,Mg)₆—MnO₈ Ni/(Li,Mg)₆—MnO₈ Na₄P₂O₇Au/Na₄P₂O₇ Mo/Na₄P₂O₇ Ni/Na₄P₂O₇ Mo₂O₈ Au/Mo₂O₈ Mo/Mo₂O₈ Ni/Mo₂O₈Mn₃O₄/WO₄ Au/Mn₃O₄/WO₄ Mo/Mn₃O₄/WO₄ Ni/Mn₃O₄/WO₄ Na₂WO₄ Au/Na₂WO₄Mo/Na₂WO₄ Ni/Na₂WO₄ Zr₂Mo₂O₈ Au/Zr₂Mo₂O₈ Mo/Zr₂Mo₂O₈ Ni/Zr₂Mo₂O₈NaMnO₄—/MgO Au/NaMnO₄—/MgO Mo/NaMnO₄—/MgO Ni/NaMnO₄—/MgO Na₁₀Mn—W₅O₁₇Au/Na₁₀Mn—W₅O₁₇ Mo/Na₁₀Mn—W₅O₁₇ Ni/Na₁₀Mn—W₅O₁₇ La₃NdO₆ Au/La₃NdO₆Mo/La₃NdO₆ Ni/La₃NdO₆ LaNd₃O₆ Au/LaNd₃O₆ Mo/LaNd₃O₆ Ni/LaNd₃O₆La_(1.5)Nd_(2.5)O₆ Au/La_(1.5)Nd_(2.5)O₆ Mo/La_(1.5)Nd_(2.5)O₆Ni/La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ Au/La_(2.5)Nd_(1.5)O₆Mo/La_(2.5)Nd_(1.5)O₆ Ni/La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆Au/La_(3.2)Nd_(0.8)O₆ Mo/La_(3.2)Nd_(0.8)O₆ Ni/La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Au/La_(3.5)Nd_(0.5)O₆ Mo/La_(3.5)Nd_(0.5)O₆Ni/La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆ Au/La_(3.8)Nd_(0.2)O₆Mo/La_(3.8)Nd_(0.2)O₆ Ni/La_(3.8)Nd_(0.2)O₆ Y—La Au/Y—La Mo/Y—La Ni/Y—LaZr—La Au/Zr—La Mo/Zr—La Ni/Zr—La Pr—La Au/Pr—La Mo/Pr—La Ni/Pr—La Ce—LaAu/Ce—La Mo/Ce—La Ni/Ce—La

TABLE 7 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Co Sb WV Ag Te Pd Ir Li₂O Co/Li₂O Sb/Li₂O W/Li₂O V/Li₂O Ag/Li₂O Te/Li₂O Pd/Li₂OIr/Li₂O Na₂O Co/Na₂O Sb/Na₂O W/Na₂O V/Na₂O Ag/Na₂O Te/Na₂O Pd/Na₂OIr/Na₂O K₂O Co/K₂O Sb/K₂O W/K₂O V/K₂O Ag/K₂O Te/K₂O Pd/K₂O Ir/K₂O Rb₂OCo/Rb₂O Sb/Rb₂O W/Rb₂O V/Rb₂O Ag/Rb₂O Te/Rb₂O Pd/Rb₂O Ir/Rb₂O Cs₂OCo/Cs₂O Sb/Cs₂O W/Cs₂O V/Cs₂O Ag/Cs₂O Te/Cs₂O Pd/Cs₂O Ir/Cs₂O BeO Co/BeOSb/BeO W/BeO V/BeO Ag/BeO Te/BeO Pd/BeO Ir/BeO MgO Co/MgO Sb/MgO W/MgOV/MgO Ag/MgO Te/MgO Pd/MgO Ir/MgO CaO Co/CaO Sb/CaO W/CaO V/CaO Ag/CaOTe/CaO Pd/CaO Ir/CaO SrO Co/SrO Sb/SrO W/SrO V/SrO Ag/SrO Te/SrO Pd/SrOIr/SrO BaO Co/BaO Sb/BaO W/BaO V/BaO Ag/BaO Te/BaO Pd/BaO Ir/BaO Sc₂O₃Co/Sc₂O₃ Sb/Sc₂O₃ W/Sc₂O₃ V/Sc₂O₃ Ag/Sc₂O₃ Te/Sc₂O₃ Pd/Sc₂O₃ Ir/Sc₂O₃Y₂O₃ Co/Y₂O₃ Sb/Y₂O₃ W/Y₂O₃ V/Y₂O₃ Ag/Y₂O₃ Te/Y₂O₃ Pd/Y₂O₃ Ir/Y₂O₃ La₂O₃Co/La₂O₃ Sb/La₂O₃ W/La₂O₃ V/La₂O₃ Ag/La₂O₃ Te/La₂O₃ Pd/La₂O₃ Ir/La₂O₃CeO₂ Co/CeO₂ Sb/CeO₂ W/CeO₂ V/CeO₂ Ag/CeO₂ Te/CeO₂ Pd/CeO₂ Ir/CeO₂ Ce₂O₃Co/Ce₂O₃ Sb/Ce₂O₃ W/Ce₂O₃ V/Ce₂O₃ Ag/Ce₂O₃ Te/Ce₂O₃ Pd/Ce₂O₃ Ir/Ce₂O₃Pr₂O₃ Co/Pr₂O₃ Sb/Pr₂O₃ W/Pr₂O₃ V/Pr₂O₃ Ag/Pr₂O₃ Te/Pr₂O₃ Pd/Pr₂O₃Ir/Pr₂O₃ Nd₂O₃ Co/Nd₂O₃ Sb/Nd₂O₃ W/Nd₂O₃ V/Nd₂O₃ Ag/Nd₂O₃ Te/Nd₂O₃Pd/Nd₂O₃ Ir/Nd₂O₃ Sm₂O₃ Co/Sm₂O₃ Sb/Sm₂O₃ W/Sm₂O₃ V/Sm₂O₃ Ag/Sm₂O₃Te/Sm₂O₃ Pd/Sm₂O₃ Ir/Sm₂O₃ Eu₂O₃ Co/Eu₂O₃ Sb/Eu₂O₃ W/Eu₂O₃ V/Eu₂O₃Ag/Eu₂O₃ Te/Eu₂O₃ Pd/Eu₂O₃ Ir/Eu₂O₃ Gd₂O₃ Co/Gd₂O₃ Sb/Gd₂O₃ W/Gd₂O₃V/Gd₂O₃ Ag/Gd₂O₃ Te/Gd₂O₃ Pd/Gd₂O₃ Ir/Gd₂O₃ Tb₂O₃ Co/Tb₂O₃ Sb/Tb₂O₃W/Tb₂O₃ V/Tb₂O₃ Ag/Tb₂O₃ Te/Tb₂O₃ Pd/Tb₂O₃ Ir/Tb₂O₃ TbO₂ Co/TbO₂ Sb/TbO₂W/TbO₂ V/TbO₂ Ag/TbO₂ Te/TbO₂ Pd/TbO₂ Ir/TbO₂ Tb₆O₁₁ Co/Tb₆O₁₁ Sb/Tb₆O₁₁W/Tb₆O₁₁ V/Tb₆O₁₁ Ag/Tb₆O₁₁ Te/Tb₆O₁₁ Pd/Tb₆O₁₁ Ir/Tb₆O₁₁ Dy₂O₃ Co/Dy₂O₃Sb/Dy₂O₃ W/Dy₂O₃ V/Dy₂O₃ Ag/Dy₂O₃ Te/Dy₂O₃ Pd/Dy₂O₃ Ir/Dy₂O₃ Ho₂O₃Co/Ho₂O₃ Sb/Ho₂O₃ W/Ho₂O₃ V/Ho₂O₃ Ag/Ho₂O₃ Te/Ho₂O₃ Pd/Ho₂O₃ Ir/Ho₂O₃Er₂O₃ Co/Er₂O₃ Sb/Er₂O₃ W/Er₂O₃ V/Er₂O₃ Ag/Er₂O₃ Te/Eu₂O₃ Pd/Er₂O₃Ir/Er₂O₃ Tm₂O₃ Co/Tm₂O₃ Sb/Tm₂O₃ W/Tm₂O₃ V/Tm₂O₃ Ag/Tm₂O₃ Te/Tm₂O₃Pd/Tm₂O₃ Ir/Tm₂O₃ Yb₂O₃ Co/Yb₂O₃ Sb/Yb₂O₃ W/Yb₂O₃ V/Yb₂O₃ Ag/Yb₂O₃Te/Yb₂O₃ Pd/Yb₂O₃ Ir/Yb₂O₃ Lu₂O₃ Co/Lu₂O₃ Sb/Lu₂O₃ W/Lu₂O₃ V/Lu₂O₃Ag/Lu₂O₃ Te/Lu₂O₃ Pd/Lu₂O₃ Ir/Lu₂O₃ Ac₂O₃ Co/Ac₂O₃ Sb/Ac₂O₃ W/Ac₂O₃V/Ac₂O₃ Ag/Ac₂O₃ Te/Ac₂O₃ Pd/Ac₂O₃ Ir/Ac₂O₃ Th₂O₃ Co/Th₂O₃ Sb/Th₂O₃W/Th₂O₃ V/Th₂O₃ Ag/Th₂O₃ Te/Th₂O₃ Pd/Th₂O₃ Ir/Th₂O₃ ThO₂ Co/ThO₂ Sb/ThO₂W/ThO₂ V/ThO₂ Ag/ThO₂ Te/ThO₂ Pd/ThO₂ Ir/ThO₂ Pa₂O₃ Co/Pa₂O₃ Sb/Pa₂O₃W/Pa₂O₃ V/Pa₂O₃ Ag/Pa₂O₃ Te/Pa₂O₃ Pd/Pa₂O₃ Ir/Pa₂O₃ PaO₂ Co/PaO₂ Sb/PaO₂W/PaO₂ V/PaO₂ Ag/PaO₂ Te/PaO₂ Pd/PaO₂ Ir/PaO₂ TiO₂ Co/TiO₂ Sb/TiO₂W/TiO₂ V/TiO₂ Ag/TiO₂ Te/TiO₂ Pd/TiO₂ Ir/TiO₂ TiO Co/TiO Sb/TiO W/TiOV/TiO Ag/TiO Te/TiO Pd/TiO Ir/TiO Ti₂O₃ Co/Ti₂O₃ Sb/Ti₂O₃ W/Ti₂O₃V/Ti₂O₃ Ag/Ti₂O₃ Te/Ti₂O₃ Pd/Ti₂O₃ Ir/Ti₂O₃ Ti₃O Co/Ti₃O Sb/Ti₃O W/Ti₃OV/Ti₃O Ag/Ti₃O Te/Ti₃O Pd/Ti₃O Ir/Ti₃O Ti₂O Co/Ti₂O Sb/Ti₂O W/Ti₂OV/Ti₂O Ag/Ti₂O Te/Ti₂O Pd/Ti₂O Ir/Ti₂O Ti₃O₅ Co/Ti₃O₅ Sb/Ti₃O₅ W/Ti₃O₅V/Ti₃O₅ Ag/Ti₃O₅ Te/Ti₃O₅ Pd/Ti₃O₅ Ir/Ti₃O₅ Ti₄O₇ Co/Ti₄O₇ Sb/Ti₄O₇W/Ti₄O₇ V/Ti₄O₇ Ag/Ti₄O₇ Te/Ti₄O₇ Pd/Ti₄O₇ Ir/Ti₄O₇ ZrO₂ Co/ZrO₂ Sb/ZrO₂W/ZrO₂ V/ZrO₂ Ag/ZrO₂ Te/ZrO₂ Pd/ZrO₂ Ir/ZrO₂ HfO₂ Co/HfO₂ Sb/HfO₂W/HfO₂ V/HfO₂ Ag/HfO₂ Te/HfO₂ Pd/HfO₂ Ir/HfO₂ VO Co/VO Sb/VO W/VO V/VOAg/VO Te/VO Pd/VO Ir/VO V₂O₃ Co/V₂O₃ Sb/V₂O₃ W/V₂O₃ V/V₂O₃ Ag/V₂O₃Te/V₂O₃ Pd/V₂O₃ Ir/V₂O₃ VO₂ Co/VO₂ Sb/VO₂ W/VO₂ V/VO₂ Ag/VO₂ Te/VO₂Pd/VO₂ Ir/VO₂ V₂O₅ Co/V₂O₅ Sb/V₂O₅ W/V₂O₅ V/V₂O₅ Ag/V₂O₅ Te/V₂O₅ Pd/V₂O₅Ir/V₂O₅ V₃O₇ Co/V₃O₇ Sb/V₃O₇ W/V₃O₇ V/V₃O₇ Ag/V₃O₇ Te/V₃O₇ Pd/V₃O₇Ir/V₃O₇ V₄O₉ Co/V₄O₉ Sb/V₄O₉ W/V₄O₉ V/V₄O₉ Ag/V₄O₉ Te/V₄O₉ Pd/V₄O₉Ir/V₄O₉ V₆O₁₃ Co/V₆O₁₃ Sb/V₆O₁₃ W/V₆O₁₃ V/V₆O₁₃ Ag/V₆O₁₃ Te/V₆O₁₃Pd/V₆O₁₃ Ir/V₆O₁₃ NbO Co/NbO Sb/NbO W/NbO V/NbO Ag/NbO Te/NbO Pd/NbOIr/NbO NbO₂ Co/NbO₂ Sb/NbO₂ W/NbO₂ V/NbO₂ Ag/NbO₂ Te/NbO₂ Pd/NbO₂Ir/NbO₂ Nb₂O₅ Co/Nb₂O₅ Sb/Nb₂O₅ W/Nb₂O₅ V/Nb₂O₅ Ag/Nb₂O₅ Te/Nb₂O₅Pd/Nb₂O₅ Ir/Nb₂O₅ Nb₈O₁₉ Co/Nb₈O₁₉ Sb/Nb₈O₁₉ W/Nb₈O₁₉ V/Nb₈O₁₉ Ag/Nb₈O₁₉Te/Nb₈O₁₉ Pd/Nb₈O₁₉ Ir/Nb₈O₁₉ Nb₁₆O₃₈ Co/Nb₁₆O₃₈ Sb/Nb₁₆O₃₈ W/Nb₁₆O₃₈V/Nb₁₆O₃₈ Ag/Nb₁₆O₃₈ Te/Nb₁₆O₃₈ Pd/Nb₁₆O₃₈ Ir/Nb₁₆O₃₈ Nb₁₂O₂₉ Co/Nb₁₂O₂₉Sb/Nb₁₂O₂₉ W/Nb₁₂O₂₉ V/Nb₁₂O₂₉ Ag/Nb₁₂O₂₉ Te/Nb₁₂O₂₉ Pd/Nb₁₂O₂₉Ir/Nb₁₂O₂₉ Nb₄₇O₁₁₆ Co/Nb₄₇O₁₁₆ Sb/Nb₄₇O₁₁₆ W/Nb₄₇O₁₁₆ V/Nb₄₇O₁₁₆Ag/Nb₄₇O₁₁₆ Te/Nb₄₇O₁₁₆ Pd/Nb₄₇O₁₁₆ Ir/Nb₄₇O₁₁₆ Ta₂O₅ Co/Ta₂O₅ Sb/Ta₂O₅W/Ta₂O₅ V/Ta₂O₅ Ag/Ta₂O₅ Te/Ta₂O₅ Pd/Ta₂O₅ Ir/Ta₂O₅ CrO Co/CrO Sb/CrOW/CrO V/CrO Ag/CrO Te/CrO Pd/CrO Ir/CrO Cr₂O₃ Co/Cr₂O₃ Sb/Cr₂O₃ W/Cr₂O₃V/Cr₂O₃ Ag/Cr₂O₃ Te/Cr₂O₃ Pd/Cr₂O₃ Ir/Cr₂O₃ CrO₂ Co/CrO₂ Sb/CrO₂ W/CrO₂V/CrO₂ Ag/CrO₂ Te/CrO₂ Pd/CrO₂ Ir/CrO₂ CrO₃ Co/CrO₃ Sb/CrO₃ W/CrO₃V/CrO₃ Ag/CrO₃ Te/CrO₃ Pd/CrO₃ Ir/CrO₃ Cr₈O₂₁ Co/Cr₈O₂₁ Sb/Cr₈O₂₁W/Cr₈O₂₁ V/Cr₈O₂₁ Ag/Cr₈O₂₁ Te/Cr₈O₂₁ Pd/Cr₈O₂₁ Ir/Cr₈O₂₁ MoO₂ Co/MoO₂Sb/MoO₂ W/MoO₂ V/MoO₂ Ag/MoO₂ Te/MoO₂ Pd/MoO₂ Ir/MoO₂ MoO₃ Co/MoO₃Sb/MoO₃ W/MoO₃ V/MoO₃ Ag/MoO₃ Te/MoO₃ Pd/MoO₃ Ir/MoO₃ W₂O₃ Co/W₂O₃Sb/W₂O₃ W/W₂O₃ V/W₂O₃ Ag/W₂O₃ Te/W₂O₃ Pd/W₂O₃ Ir/W₂O₃ WoO₂ Co/WoO₂Sb/WoO₂ W/WoO₂ V/WoO₂ Ag/WoO₂ Te/WoO₂ Pd/WoO₂ Ir/WoO₂ WoO₃ Co/WoO₃Sb/WoO₃ W/WoO₃ V/WoO₃ Ag/WoO₃ Te/WoO₃ Pd/WoO₃ Ir/WoO₃ MnO Co/MnO Sb/MnOW/MnO V/MnO Ag/MnO Te/MnO Pd/MnO Ir/MnO Mn/Mg/O Co/Mn/Mg/O Sb/Mn/Mg/OW/Mn/Mg/O V/Mn/Mg/O Ag/Mn/Mg/O Te/Mn/Mg/O Pd/Mn/Mg/O Ir/Mn/Mg/O Mn₃O₄Co/Mn₃O₄ Sb/Mn₃O₄ W/Mn₃O₄ V/Mn₃O₄ Ag/Mn₃O₄ Te/Mn₃O₄ Pd/Mn₃O₄ Ir/Mn₃O₄Mn₂O₃ Co/Mn₂O₃ Sb/Mn₂O₃ W/Mn₂O₃ V/Mn₂O₃ Ag/Mn₂O₃ Te/Mn₂O₃ Pd/Mn₂O₃Ir/Mn₂O₃ MnO₂ Co/MnO₂ Sb/MnO₂ W/MnO₂ V/MnO₂ Ag/MnO₂ Te/MnO₂ Pd/MnO₂Ir/MnO₂ Mn₂O₇ Co/Mn₂O₇ Sb/Mn₂O₇ W/Mn₂O₇ V/Mn₂O₇ Ag/Mn₂O₇ Te/Mn₂O₇Pd/Mn₂O₇ Ir/Mn₂O₇ ReO₂ Co/ReO₂ Sb/ReO₂ W/ReO₂ V/ReO₂ Ag/ReO₂ Te/ReO₂Pd/ReO₂ Ir/ReO₂ ReO₃ Co/ReO₃ Sb/ReO₃ W/ReO₃ V/ReO₃ Ag/ReO₃ Te/ReO₃Pd/ReO₃ Ir/ReO₃ Re₂O₇ Co/Re₂O₇ Sb/Re₂O₇ W/Re₂O₇ V/Re₂O₇ Ag/Re₂O₇Te/Re₂O₇ Pd/Re₂O₇ Ir/Re₂O₇ Mg₃Mn₃—B₂O₁₀ Co/Mg₃Mn₃—B₂O₁₀ Sb/Mg₃Mn₃—B₂O₁₀W/Mg₃Mn₃—B₂O₁₀ V/Mg₃Mn₃—B₂O₁₀ Ag/Mg₃Mn₃—B₂O₁₀ Te/Mg₃Mn₃—B₂O₁₀Pd/Mg₃Mn₃—B₂O₁₀ Ir/Mg₃Mn₃—B₂O₁₀ Mg₃(BO₃)₂ Co/Mg₃(BO₃)₂ Sb/Mg₃(BO₃)₂W/Mg₃(BO₃)₂ V/Mg₃(BO₃)₂ Ag/Mg₃(BO₃)₂ Te/Mg₃(BO₃)₂ Pd/Mg₃(BO₃)₂Ir/Mg₃(BO₃)₂ NaWO₄ Co/NaWO₄ Sb/NaWO₄ W/NaWO₄ V/NaWO₄ Ag/NaWO₄ Te/NaWO₄Pd/NaWO₄ Ir/NaWO₄ Mg₆MnO₈ Co/Mg₆MnO₈ Sb/Mg₆MnO₈ W/Mg₆MnO₈ V/Mg₆MnO₈Ag/Mg₆MnO₈ Te/Mg₆MnO₈ Pd/Mg₆MnO₈ Ir/Mg₆MnO₈ Mn₂O₄ Co/Mn₂O₄ Sb/Mn₂O₄W/Mn₂O₄ V/Mn₂O₄ Ag/Mn₂O₄ Te/Mn₂O₄ Pd/Mn₂O₄ Ir/Mn₂O₄ (Li,Mg)₆—MnO₈Co/(Li,Mg)₆—MnO₈ Sb/(Li,Mg)₆—MnO₈ W/(Li,Mg)₆—MnO₈ V/(Li,Mg)₆—MnO₈Ag/(Li,Mg)₆—MnO₈ Te/(Li,Mg)₆—MnO₈ Pd/(Li,Mg)₆—MnO₈ Ir/(Li,Mg)₆—MnO₈Na₄P₂O₇ Co/Na₄P₂O₇ Sb/Na₄P₂O₇ W/Na₄P₂O₇ V/Na₄P₂O₇ Ag/Na₄P₂O₇ Te/Na₄P₂O₇Pd/Na₄P₂O₇ Ir/Na₄P₂O₇ Mo₂O₈ Co/Mo₂O₈ Sb/Mo₂O₈ W/Mo₂O₈ V/Mo₂O₈ Ag/Mo₂O₈Te/Mo₂O₈ Pd/Mo₂O₈ Ir/Mo₂O₈ Mn₃O₄/WO₄ Co/Mn₃O₄/WO₄ Sb/Mn₃O₄/WO₄W/Mn₃O₄/WO₄ V/Mn₃O₄/WO₄ Ag/Mn₃O₄/WO₄ Te/Mn₃O₄/WO₄ Pd/Mn₃O₄/WO₄Ir/Mn₃O₄/WO₄ Na₂WO₄ Co/Na₂WO₄ Sb/Na₂WO₄ W/Na₂WO₄ V/Na₂WO₄ Ag/Na₂WO₄Te/Na₂WO₄ Pd/Na₂WO₄ Ir/Na₂WO₄ Zr₂Mo₂O₈ Co/Zr₂Mo₂O₈ Sb/Zr₂Mo₂O₈W/Zr₂Mo₂O₈ V/Zr₂Mo₂O₈ Ag/Zr₂Mo₂O₈ Te/Zr₂Mo₂O₈ Pd/Zr₂Mo₂O₈ Ir/Zr₂Mo₂O₈NaMnO₄—/MgO Co/NaMnO₄—/MgO Sb/NaMnO₄—/MgO W/NaMnO₄—/MgO V/NaMnO₄—/MgOAg/NaMnO₄—/MgO Te/NaMnO₄—/MgO Pd/NaMnO₄—/MgO Ir/NaMnO₄—/MgO Na₁₀Mn—W₅O₁₇Co/Na₁₀Mn—W₅O₁₇ Sb/Na₁₀Mn—W₅O₁₇ W/Na₁₀Mn—W₅O₁₇ V/Na₁₀Mn—W₅O₁₇Ag/Na₁₀Mn—W₅O₁₇ Te/Na₁₀Mn—W₅O₁₇ Pd/Na₁₀Mn—W₅O₁₇ Ir/Na₁₀Mn—W₅O₁₇ La₃NdO₆Co/La₃NdO₆ Sb/La₃NdO₆ W/La₃NdO₆ V/La₃NdO₆ Ag/La₃NdO₆ Te/La₃NdO₆Pd/La₃NdO₆ Ir/La₃NdO₆ LaNd₃O₆ Co/LaNd₃O₆ Sb/LaNd₃O₆ W/LaNd₃O₆ V/LaNd₃O₆Ag/LaNd₃O₆ Te/LaNd₃O₆ Pd/LaNd₃O₆ Ir/LaNd₃O₆ La_(1.5)Nd_(2.5)O₆Co/La_(1.5)Nd_(2.5)O₆ Sb/La_(1.5)Nd_(2.5)O₆ W/La_(1.5)Nd_(2.5)O₆V/La_(1.5)Nd_(2.5)O₆ Ag/La_(1.5)Nd_(2.5)O₆ Te/La_(1.5)Nd_(2.5)O₆Pd/La_(1.5)Nd_(2.5)O₆ Ir/La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆Co/La_(2.5)Nd_(1.5)O₆ Sb/La_(2.5)Nd_(1.5)O₆ W/La_(2.5)Nd_(1.5)O₆V/La_(2.5)Nd_(1.5)O₆ Ag/La_(2.5)Nd_(1.5)O₆ Te/La_(2.5)Nd_(1.5)O₆Pd/La_(2.5)Nd_(1.5)O₆ Ir/La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆Co/La_(3.2)Nd_(0.8)O₆ Sb/La_(3.2)Nd_(0.8)O₆ W/La_(3.2)Nd_(0.8)O₆V/La_(3.2)Nd_(0.8)O₆ Ag/La_(3.2)Nd_(0.8)O₆ Te/La_(3.2)Nd_(0.8)O₆Pd/La_(3.2)Nd_(0.8)O₆ Ir/La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆Co/La_(3.5)Nd_(0.5)O₆ Sb/La_(3.5)Nd_(0.5)O₆ W/La_(3.5)Nd_(0.5)O₆V/La_(3.5)Nd_(0.5)O₆ Ag/La_(3.5)Nd_(0.5)O₆ Te/La_(3.5)Nd_(0.5)O₆Pd/La_(3.5)Nd_(0.5)O₆ Ir/La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆Co/La_(3.8)Nd_(0.2)O₆ Sb/La_(3.8)Nd_(0.2)O₆ W/La_(3.8)Nd_(0.2)O₆V/La_(3.8)Nd_(0.2)O₆ Ag/La_(3.8)Nd_(0.2)O₆ Te/La_(3.8)Nd_(0.2)O₆Pd/La_(3.8)Nd_(0.2)O₆ Ir/La_(3.8)Nd_(0.2)O₆ Y—La Co/Y—La Sb/Y—La W/Y—LaV/Y—La Ag/Y—La Te/Y—La Pd/Y—La Ir/Y—La Zr—La Co/Zr—La Sb/Zr—La W/Zr—LaV/Zr—La Ag/Zr—La Te/Zr—La Pd/Zr—La Ir/Zr—La Pr—La Co/Pr—La Sb/Pr—LaW/Pr—La V/Pr—La Ag/Pr—La Te/Pr—La Pd/Pr—La Ir/Pr—La Ce—La Co/Ce—LaSb/Ce—La W/Ce—La V/Ce—La Ag/Ce—La Te/Ce—La Pd/Ce—La Ir/Ce—La

TABLE 8 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) NW\Dop Mn TiLi₂O Mn/ Ti/ Li₂O Li₂O Na₂O Mn/ Ti/ Na₂O Na₂O K₂O Mn/ Ti/ K₂O K₂O Rb₂OMn/ Ti/ Rb₂O Rb₂O Cs₂O Mn/ Ti/ Cs₂O Cs₂O BeO Mn/ Ti/ BeO BeO MgO Mn/ Ti/MgO MgO CaO Mn/ Ti/ CaO CaO SrO Mn/ Ti/ SrO SrO BaO Mn/ Ti/ BaO BaOSc₂O₃ Mn/ Ti/ Sc₂O₃ Sc₂O₃ Y₂O₃ Mn/ Ti/ Y₂0₃ Y₂0₃ La₂O₃ Mn/ Ti/ La₂O₃La₂O₃ CeO₂ Mn/ Ti/ CeO₂ CeO₂ Ce₂O₃ Mn/ Ti/ Ce₂O₃ Ce₂O₃ Pr₂O₃ Mn/ Ti/Pr₂O₃ Pr₂O₃ Nd₂O₃ Mn/ Ti/ Nd₂O₃ Nd₂O₃ Sm₂O₃ Mn/ Ti/ Sm₂O₃ Sm₂O₃ Eu₂O₃Mn/ Ti/ Eu₂O₃ Eu₂O₃ Gd₂O₃ Mn/ Ti/ Gd₂O₃ Gd₂O₃ Tb₂O₃ Mn/ Ti/ Tb₂O₃ Tb₂O₃TbO₂ Mn/ Ti/ TbO₂ TbO₂ Tb₆O₁₁ Mn/ Ti/ Tb₆O₁₁ Tb₆O₁₁ Dy₂O₃ Mn/ Ti/ Dy₂O₃Dy₂O₃ Ho₂O₃ Mn/ Ti/ Ho₂O₃ Ho₂O₃ Er₂O₃ Mn/ Ti/ Er₂O₃ Er₂O₃ Tm₂O₃ Mn/ Ti/Tm₂O₃ Tm₂O₃ Yb₂O₃ Mn/ Ti/ Yb₂O₃ Yb₂O₃ Lu₂O₃ Mn/ Ti/ Lu₂O₃ Lu₂O₃ Ac₂O₃Mn/ Ti/ Ac₂O₃ Ac₂O₃ Th₂O₃ Mn/ Ti/ Th₂O₃ Th₂O₃ ThO₂ Mn/ Ti/ ThO₂ ThO₂Pa₂O₃ Mn/ Ti/ Pa₂O₃ Pa₂O₃ PaO₂ Mn/ Ti/ PaO₂ PaO₂ TiO₂ Mn/ Ti/ TiO₂ TiO₂TiO Mn/ Ti/ TiO TiO Ti₂O₃ Mn/ Ti/ Ti₂O₃ Ti₂O₃ Ti₃O Mn/ Ti/ Ti₃O Ti₃OTi₂O Mn/ Ti/ Ti₂O Ti₂O Ti₃O₅ Mn/ Ti/ Ti₃O₅ Ti₃O₅ Ti₄O₇ Mn/ Ti/ Ti₄O₇Ti₄O₇ ZrO₂ Mn/ Ti/ ZrO₂ ZrO₂ HfO₂ Mn/ Ti/ HfO₂ HfO₂ VO Mn/ Ti/ VO VOV₂O₃ Mn/ Ti/ V₂O₃ V₂O₃ VO₂ Mn/ Ti/ VO₂ VO₂ V₂O₅ Mn/ Ti/ V₂O₅ V₂O₅ V₃O₇Mn/ Ti/ V₃O₇ V₃O₇ V₄O₉ Mn/ Ti/ V₄O₉ V₄O₉ V₆O₁₃ Mn/ Ti/ V₆O₁₃ V₆O₁₃ NbOMn/ Ti/ NbO NbO NbO₂ Mn/ Ti/ NbO₂ NbO₂ Nb₂O₅ Mn/ Ti/ Nb₂O₅ Nb₂O₅ Nb₈O₁₉Mn/ Ti/ Nb₈O₁₉ Nb₈O₁₉ Nb₁₆O₃₈ Mn/ Ti/ Nb₁₆O₃₈ Nb₁₆O₃₈ Nb₁₂O₂₉ Mn/ Ti/Nb₁₂O₂₉ Nb₁₂O₂₉ Nb₄₇O₁₁₆ Mn/ Ti/ Nb₄₇O₁₁₆ Nb₄₇O₁₁₆ Ta₂O₅ Mn/ Ti/ Ta₂O₅Ta₂O₅ CrO Mn/ Ti/ CrO CrO Cr₂O₃ Mn/ Ti/ Cr₂O₃ Cr₂O₃ CrO₂ Mn/ Ti/ CrO₂CrO₂ CrO₃ Mn/ Ti/ CrO₃ CrO₃ Cr₈O₂₁ Mn/ Ti/ Cr₈O₂₁ Cr₈O₂₁ MoO₂ Mn/ Ti/MoO₂ MoO₂ MoO₃ Mn/ Ti/ MoO₃ MoO₃ W₂O₃ Mn/ Ti/ W₂O₃ W₂O₃ WoO₂ Mn/ Ti/WoO₂ WoO₂ WoO₃ Mn/ Ti/ WoO₃ WoO₃ MnO Mn/ Ti/ MnO MnO Mn/Mg/O Mn/ Ti/Mn/Mg/O Mn/Mg/O Mn₃O₄ Mn/ Ti/ Mn₃O₄ Mn₃O₄ Mn₂O₃ Mn/ Ti/ Mn₂O₃ Mn₂O₃ MnO₂Mn/ Ti/ MnO₂ MnO₂ Mn₂O₇ Mn/ Ti/ Mn₂O₇ Mn₂O₇ ReO₂ Mn/ Ti/ ReO₂ ReO₂ ReO₃Mn/ Ti/ ReO₃ ReO₃ Re₂O₇ Mn/ Ti/ Re₂O₇ Re₂O₇ Mg₃Mn₃— Mn/ Ti/ B₂O₁₀Mg₃Mn₃— Mg₃Mn₃— B₂O₁₀ B₂O₁₀ Mg₃(BO₃)₂ Mn/ Ti/ Mg₃(BO₃)₂ Mg₃(BO₃)₂ NaWO₄Mn/ Ti/ NaWO₄ NaWO₄ Mg₆MnO₈ Mn/ Ti/ Mg₆MnO₈ Mg₆MnO₈ Mn₂O₄ Mn/ Ti/ Mn₂O₄Mn₂O₄ (Li,Mg)₆— Mn/ Mn/ MnO₈ (Li,Mg)₆— (Li,Mg)₆— MnO₈ MnO₈ Na₄P₂O₇ Mn/Ti/ Na₄P₂O₇ Na₄P₂O₇ Mo₂O₈ Mn/ Ti/ Mo₂O₈ Mo₂O₈ Mn₃O₄/WO₄ Mn/ Ti/Mn₃O₄/WO₄ Mn₃O₄/WO₄ Na₂WO₄ Mn/ Ti/ Na₂WO₄ Na₂WO₄ Zr₂Mo₂O₈ Mn/ Ti/Zr₂Mo₂O₈ Zr₂Mo₂O₈ NaMnO₄—/ Mn/ Ti/ MgO NaMnO₄—/ NaMnO₄—/ MgO MgO Na₁₀Mn—Mn/ Ti/ W₅O₁₇ Na₁₀Mn— Na₁₀Mn— W₅O₁₇ W₅O₁₇ La₃NdO₆ Mn/ Ti/ La₃NdO₆La₃NdO₆ LaNd₃O₆ Mn/ Ti/ LaNd₃O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ Mn/ Ti/La_(1.5)Nd_(2.5)O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ Mn/ Ti/La_(2.5)Nd_(1.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ Mn/ Ti/La_(3.2)Nd_(0.8)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mn/ Ti/La_(3.5)Nd_(0.5)O₆ La_(3.5)Nd_(0.5)O₆ La_(3.8)Nd_(0.2)O₆ Mn/ Ti/La_(3.8)Nd_(0.2)O₆ La_(3.8)Nd_(0.2)O₆ Y—La Mn/ Ti/ Y—La Y—La Zr—La Mn/Ti/ Zr—La Zr—La Pr—La Mn/ Ti/ Pr—La Pr—La Ce—La Mn/ Ti/ Ce—La Ce—La

TABLE 9 Nanowires (NW) Doped With Specific Dopants (Dop) Dop\NW La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Na Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Na Sr/Na/ Sr/Na/ Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Zr/Eu/CaNa/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Na Mg/Na/ Mg/Na/Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/WSr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/K/Mg/TmNa/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/La/Eu Na/La/Eu/ Na/La/Eu/Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/CeSr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃Rb/Sr/ Na/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/La/Li/Cs Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/La K/La/ K/La/ K/La/ K/La/ K/La/ K/La/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/La/S K/La/S/ K/La/S/ K/La/S/K/La/S/ K/La/S/ K/La/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ K/Na K/Na/K/Na/ K/Na/ K/Na/ K/Na/ K/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/Li/Cs/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Cs/La/Tm Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Li/Sr/Zn/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Ga/Cs Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Rb/Ga Li/Na/Rb/Ga/ Li/Na/Rb/Ga/Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Na/Sr/LaLi/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sm/Cs Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/K/LaCs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Cs/Li/K/La Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/Cs/Li/K/La/ Cs/Li/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Cs/LaSr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Ho/TmSr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd/S La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/La/Nd/S/ La/Nd/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Rb/CaLi/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K Li/K/ Li/K/ Li/K/ Li/K/ Li/K/ Li/K/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ Rb/Sr/ Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Sr/Lu/NbNa/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Eu/Hf Na/Eu/Hf/Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Pt/BiNa/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/Rb/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/Ca/Cs/ Ca/Cs/ Ca/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Mg/NaCa/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/Hf/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Sr/Sn/ Sr/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Pr/KSr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ Rb/Sr/ Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/Sr/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/W Zr/W/ Zr/W/ Zr/W/Zr/W/ Zr/W/ Zr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Y/W Y/W/ Y/W/Y/W/ Y/W/ Y/W/ Y/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/W Na/W/Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/WBi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Ca Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/Bi/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/Bi/Sn/ Bi/Sn/ Bi/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Sb Bi/Sb/Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/Sb/Bi/ Sb/Bi/ Sb/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Au Sb/Au/Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sb/Sm Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/Sr/Tb/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/Sb/Sr/ Sb/Sr/ Sb/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/W Sb/W/Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/Sb/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Au Yb/Au/ Yb/Au/ Yb/Au/Yb/Au/ Yb/Au/ Yb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Ta Yb/Ta/Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/Yb/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/W Yb/W/ Yb/W/ Yb/W/Yb/W/ Yb/W/ Yb/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb/Ag Yb/Ag/Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/Sr/Hf/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ W/Ge W/Ge/ W/Ge/ W/Ge/W/Ge/ W/Ge/ W/Ge/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ta/Sr Ta/Sr/Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ W/Au W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/W Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Li Sm/Li/ Sm/Li/ Sm/Li/Sm/Li/ Sm/Li/ Sm/Li/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/K La/K/La/K/ La/K/ La/K/ La/K/ La/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/Na/K/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Cs Zr/Cs/ Zr/Cs/Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/CeCa/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/Na/Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Sr Li/Sr/ Li/Sr/Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/Sr/Pr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/ Dy/K Dy/K/ Dy/K/ Dy/K/ Dy/K/Dy/K/ Dy/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Mg La/Mg/ La/Mg/La/Mg/ La/Mg/ La/Mg/ La/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/Na/Nd/In/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ In/Sr In/Sr/ In/Sr/In/Sr/ In/Sr/ In/Sr/ In/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/CsSr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ga/CsGa/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/FeLu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/La/Dy/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Li/Sr Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/K Zr/K/ Zr/K/ Zr/K/ Zr/K/ Zr/K/Zr/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃Rb/Sr/ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/Li/K/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ce/Zr/La Ce/Zr/La/Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ca/Al/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Zn/LaSr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ In/K In/K/ In/K/ In/K/ In/K/ In/K/ In/K/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Cs/La/Na Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/Cs/La/Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/S/Sr La/S/Sr/La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/TlLu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Sr/Eu/Ca Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/BSr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/K/Cs/Sr/La K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/K/Cs/Sr/La/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Sr/Lu Na/Sr/Lu/Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/K/LuRb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Ce Na/Ce/ Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Rh/TaBa/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/Ba/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Al/Bi Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/Cs/Eu/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na/Ca/LuNa/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cu/Sn Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/Cu/Sn/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ag/Au Ag/Au/ Ag/Au/ Ag/Au/Ag/Au/ Ag/Au/ Ag/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Al/Bi Al/Bi/Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/Ga/Bi/ Ga/Bi/ Ga/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/W Mg/W/Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/Zn/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Sr/Ta/ Sr/Ta/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Na Na/ Na/Na/ Na/ Na/ Na/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr Sr/ Sr/ Sr/ Sr/Sr/ Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca Ca/ Ca/ Ca/ Ca/ Ca/ Ca/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Yb Yb/ Yb/ Yb/ Yb/ Yb/ Yb/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Cs Cs/ Cs/ Cs/ Cs/ Cs/ Cs/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sb Sb/ Sb/ Sb/ Sb/ Sb/ Sb/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/Zr/Bi/ Zr/Bi/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ho/Sr Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Gd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ca/Sr/ Ca/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr/W Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Ho/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Tm/Na La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/Sr/W/Li/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃La₃NdO₆ Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ La₂O₃ Nd₂O₃Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Sr/W Sr/W/ Sr/W/ Sr/W/Sr/W/ Sr/W/ Sr/W/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd La/Nd/La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ La/Ce La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/La/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Nd/Sr La/Nd/Sr/La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Ce/Nd/SrLa/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/Eu/Sm/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/Eu/Sr/ Eu/Sr/ Eu/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Sr Mg/Sr/Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Ce/Mg Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ La₂O₃Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/Au/Pb/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/Bi/Hf/ Bi/Hf/ Bi/Hf/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/S Rb/S/Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃Sm₂O₃ La₃NdO₆ Eu/Y Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/La/Mg/ La/Mg/ La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ La₃NdO₆ Mg/Nd/Fe Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ La₂O₃ Nd₂O₃ Yb₂O₃Eu₂O₃ Sm₂O₃ La₃NdO₆ Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/La₂O₃ Nd₂O₃ Yb₂O₃ Eu₂O₃ Sm₂O₃ Rb/Sr/

TABLE 10 Nanowires (NW) Doped With Specific Dopants (Dop) Dop\NWLa_(4-X)Nd_(X)O₆* LaNd₃O₆ La_(1.5)Nd₂.₅O₆ La₂.₅Nd_(1.5)O₆La₃.₂Nd_(0.8)O₆ La₃.₅Nd_(0.5)O₆ Eu/Na Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Na Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/Sr/Na/ Sr/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Zr/Eu/CaNa/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/Na Mg/Na/Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ La_(4-X)Nd_(X)XO₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/La/K Mg/La/K/ Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ Mg/La/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/K/Mg/TmNa/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/B Sr/B/Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/Na/La/Dy/ Na/La/Dy/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/EuNa/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/Eu/In Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/K Na/La/K/ Na/La/K/ Na/La/K/Na/La/K/ Na/La/K/ Na/La/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/La/Li/CsNa/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/Na/La/Li/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/La K/La/K/La/ K/La/ K/La/ K/La/ K/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/K/La/S/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/Na K/Na/ K/Na/ K/Na/ K/Na/ K/Na/K/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/Li/Cs/ Li/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/LaLi/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/La/Tm Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Na Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/ Li/Na/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Na/Rb/Ga Li/Na/Rb/Ga/Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sm/Cs Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Sm/Yb/SBa/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Cs/K/La Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/ Cs/K/La/Cs/K/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Pr/K Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/La/Tm/NaCs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/Li/K/LaCs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Li/Sr/Cs Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs/La Sr/Cs/La/ Sr/Cs/La/Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/ Zn/K/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/Cs/K/La Zr/Cs/K/La/ Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/Sr/Ho/Tm/ Sr/Ho/Tm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Nd/SLa/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Hf/Rb Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/Sr/Hf/Rb/ Sr/Hf/Rb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Rb/CaLi/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/K Li/K/ Li/K/ Li/K/ Li/K/ Li/K/Li/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Sr/Lu Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Lu/NbNa/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Eu/HfNa/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/Na/Pt/Bi/ Na/Pt/Bi/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Hf Rb/Hf/Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ Rb/Hf/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ca/Cs Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Sr/Sn/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/ Zr/W/Zr/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Hf/K Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Y/W Y/W/ Y/W/Y/W/ Y/W/ Y/W/ Y/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/W Na/W/Na/W/ Na/W/ Na/W/ Na/W/ Na/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/ Bi/W/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/ Bi/Cs/Bi/Cs/ Bi/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Ca Bi/Ca/Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/Bi/Sb/ Bi/Sb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ge/Hf Ge/Hf/Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ Sb/Ag/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Bi Sb/Bi/Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Au Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/ Sb/Au/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/Sr/Zr/ Sr/Zr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Sm Sb/Sm/Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/Sb/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/Sb/Hf/ Sb/Hf/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb/Yb Sb/Yb/Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ Sb/Yb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/Yb/Au/ Yb/Au/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Ta Yb/Ta/Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ Yb/Ta/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Sr Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/Yb/Sr/ Yb/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Pb Yb/Pb/Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/Yb/Ag/ Yb/Ag/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Sr Au/Sr/Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ W/Ge W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/ W/Ge/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/Ta/Sr/ Ta/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ta/Hf Ta/Hf/Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ Ta/Hf/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ W/Au W/Au/ W/Au/ W/Au/ W/Au/ W/Au/ W/Au/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ Sr/Tb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/W Ca/W/Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ca/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/Sm/Li/ Sm/Li/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/K La/K/La/K/ La/K/ La/K/ La/K/ La/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/Cs Zr/Cs/Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Li/Cs Na/Li/Cs/ Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/La/Dy/K/ La/Dy/K/ La/Dy/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Dy/K Dy/K/Dy/K/ Dy/K/ Dy/K/ Dy/K/ Dy/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/ In/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/Sr/Cs/ Sr/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ce Sr/Ce/Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/Sr/Tm/ Sr/Tm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Dy La/Dy/La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/ Mg/K/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/Li/Cs/Tm/ Li/Cs/Tm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Zr/K Zr/K/Zr/K/ Zr/K/ Zr/K/ Zr/K/ Zr/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Li/K/La Li/K/La/ Li/K/La/ Li/K/La/Li/K/La/ Li/K/La/ Li/K/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ce/Zr/LaCe/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Al/La Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Zn/La Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/Sr/Zn/La/ Sr/Zn/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Cs/ZnSr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/ Sm/Cs/Sm/Cs/ Sm/Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ In/K In/K/In/K/ In/K/ In/K/ In/K/ In/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Cs/La/Na Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Cs/La/Na/Cs/La/Na/ Cs/La/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/S/SrLa/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Lu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/Pr/Zn/ Pr/Zn/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Sr/LaRb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/Na/Sr/Eu/Ca/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ K/Cs/Sr/LaK/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/La/Dy/Gd/ La/Dy/Gd/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Mg/T1/PNa/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/Na/Pt/ Na/Pt/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Li/KGd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/Rb/K/Lu/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/La/Dy/S Sr/La/Dy/S/ Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ Na/Ce/Co/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na/Ce Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ Na/Ce/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ba/Rh/Ta Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/Ba/Rh/Ta/ Ba/Rh/Ta/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ba/Ta Ba/Ta/Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs/Eu/SCs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Hf/Zr/TaHf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Gd/Li/KRb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/Na/Ca/Lu/ Na/Ca/Lu/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cu/Sn Cu/Sn/Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/Al/Bi/ Al/Bi/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Al/Mo Al/Mo/Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ Au/Pt/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ga/Bi Ga/Bi/Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/ Mg/W/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Pb/Au Pb/Au/ Pb/Au/ Pb/Au/ Pb/Au/Pb/Au/ Pb/Au/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sn/Mg Sn/Mg/Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Sr/Ta/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Na Na/ Na/ Na/Na/ Na/ Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr Sr/ Sr/ Sr/Sr/ Sr/ Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca Ca/ Ca/ Ca/Ca/ Ca/ Ca/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Yb Yb/ Yb/ Yb/Yb/ Yb/ Yb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Cs Cs/ Cs/ Cs/Cs/ Cs/ Cs/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sb Sb/ Sb/ Sb/Sb/ Sb/ Sb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho Gd/Ho/Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Gd/Ho/SrGd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ca/Sr/ Ca/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Na/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Ho/Tm/Na Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W/Li Sr/W/Li/ Sr/W/Li/ Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(4-X)Nd_(X)O₆LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/Au/Re/ Au/Re/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/W Sr/W/Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/La/Sm/ La/Sm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Ce La/Ce/La/Ce/ La/Ce/ La/Ce/ La/Ce/ La/Ce/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/ La/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Ce/Nd/SrLa/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Eu/Gd Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/Ca/Na/ Ca/Na/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Eu/Sm Eu/Sm/Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Gd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/Au/Pb/ Au/Pb/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Bi/Hf Bi/Hf/Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/ Rb/S/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Sr/Nd Sr/Nd/ Sr/Nd/ Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Eu/Y Eu/Y/Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La_(4-X)Nd_(X)O₆ LaNd₃O₆La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆La_(3.5)Nd_(0.5)O₆ Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/La/Mg/ La/Mg/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Mg/Nd/FeMg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆ La_(2.5)Nd_(1.5)O₆La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/Rb/Sr/ Rb/Sr/ La_(4-X)Nd_(X)O₆ LaNd₃O₆ La_(1.5)Nd_(2.5)O₆La_(2.5)Nd_(1.5)O₆ La_(3.2)Nd_(0.8)O₆ La_(3.5)Nd_(0.5)O₆ *x is a numberranging from greater than 0 to less than 4

TABLE 11 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop\NWLa_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/Na Eu/Na/ Eu/Na/ Eu/Na/Eu/Na/ Eu/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Na Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ Sr/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Na/Zr/Eu/Ca/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—Laa Ce—La Mg/Na Mg/Na/Mg/Na/ Mg/Na/ Mg/Na/ Mg/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Sm/Ho/Tm Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/Sr/Sm/Ho/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/W Sr/W/ Sr/W/Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/La/KMg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ Mg/La/K/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/Na/K/Mg/Tm/ Na/K/Mg/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Dy/K Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ Na/Dy/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/La/Dy Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/Na/La/Dy/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/La/Eu Na/La/Eu/Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ Na/La/Eu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Na/La/Eu/In Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/Na/La/Eu/In/ Na/La/Eu/In/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/La/Li/Cs Na/La/Li/Cs/ Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La K/La K/La/ K/La/ K/La/ K/La/ K/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La K/La/S K/La/S/ K/La/S/ K/La/S/ K/La/S/ K/La/S/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La K/Na K/Na/ K/Na/ K/Na/ K/Na/K/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs Li/Cs/ Li/Cs/Li/Cs/ Li/Cs/ Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/LaLi/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Pr/K Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/Sr/Pr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/La/TmLi/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/ Li/Cs/La/Tm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs/Sr/Tm Li/Cs/Sr/Tm/Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Li/Sr/Cs Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/Li/Sr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Sr/Zn/KLi/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Ga/Cs Li/Ga/Cs/ Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na Li/Na/ Li/Na/ Li/Na/Li/Na/ Li/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na/Rb/GaLi/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Na/Sr Li/Na/Sr/ Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Li/Na/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Sm/CsLi/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaBa/Tm/K/La Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ba/Tm/Zn/K Ba/Tm/Zn/K/Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sr/Tb/K Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La C + s/K/La Cs/K/La/ Cs/K/La/Cs/K/La/ Cs/K/La/ Cs/K/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Cs/La/Tm/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs/Li/K/LaCs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sm/Li/Sr/Cs Sm/Li/Sr/Cs/Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Cs/La Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/Sr/Cs/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Tm/Li/CsSr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zn/K Zn/K/ Zn/K/ Zn/K/ Zn/K/Zn/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zr/Cs/K/La Zr/Cs/K/La/Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Nd/S La/Nd/S/ La/Nd/S/La/Nd/S/ La/Nd/S/ La/Nd/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLi/Rb/Ca Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/K Li/K/ Li/K/ Li/K/ Li/K/Li/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Tm/Lu/Ta/P Tm/Lu/Ta/P/Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Ca/Dy/P Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaMg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Mg/La/Yb/Zn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/Sr/LuRb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/B Sr/B/ Sr/B/ Sr/B/ Sr/B/ Sr/B/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Sr/Lu/Nb Na/Sr/Lu/Nb/Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/Eu/Hf Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/Na/Eu/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Dy/Rb/Gd Dy/Rb/Gd/Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/Hf Rb/Hf/ Rb/Hf/ Rb/Hf/Rb/Hf/ Rb/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/Cs Ca/Cs/Ca/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/Hf/Bi/ Hf/Bi/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Sn Sr/Sn/Sr/Sn/ Sr/Sn/ Sr/Sn/ Sr/Sn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sr/Nb Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ Sr/Nb/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Zr/W Zr/W/ Zr/W/ Zr/W/ Zr/W/ Zr/W/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Y/W Y/W/ Y/W/ Y/W/ Y/W/ Y/W/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Na/W Na/W/ Na/W/ Na/W/ Na/W/ Na/W/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/Bi/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/Cs Bi/Cs/ Bi/Cs/Bi/Cs/ Bi/Cs/ Bi/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/CaBi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ Bi/Ca/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Bi/Sn Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/ Bi/Sn/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Bi/Sb Bi/Sb/ Bi/Sb/ Bi/Sb/Bi/Sb/ Bi/Sb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ge/Hf Ge/Hf/Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaHf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ Sb/Ag/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sb/Bi Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/ Sb/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Au Sb/Au/ Sb/Au/ Sb/Au/Sb/Au/ Sb/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Sm Sb/Sm/Sb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/ Sb/W/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/ Sb/Hf/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb/Yb Sb/Yb/ Sb/Yb/ Sb/Yb/Sb/Yb/ Sb/Yb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf/K Sr/Hf/K/Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/Yb/Ta/ Yb/Ta/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/W Yb/W/ Yb/W/Yb/W/ Yb/W/ Yb/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb/Sr Yb/Sr/Yb/Sr/ Yb/Sr/ Yb/Sr/ Yb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaYb/Pb Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Yb/W/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/Sr Au/Sr/ Au/Sr/ Au/Sr/Au/Sr/ Au/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La W/Ge W/Ge/ W/Ge/W/Ge/ W/Ge/ W/Ge/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf/RbSr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ta/Sr Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/ Ta/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ta/Hf Ta/Hf/ Ta/Hf/ Ta/Hf/Ta/Hf/ Ta/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La W/Au W/Au/ W/Au/W/Au/ W/Au/ W/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/W Ca/W/Ca/W/ Ca/W/ Ca/W/ Ca/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/ReAu/Re/ Au/Re/ Au/Re/ Au/Re/ Au/Re/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La La/K La/K/ La/K/ La/K/ La/K/ La/K/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Zn/Cs Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/ Zn/Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/K/Mg Na/K/Mg/ Na/K/Mg/Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaZr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ Ca/Ce/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Zr/K Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/Sr/Zr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Li/Cs Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/La/Dy/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Dy/K Dy/K/ Dy/K/Dy/K/ Dy/K/ Dy/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Mg La/Mg/La/Mg/ La/Mg/ La/Mg/ La/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Nd/In/K Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La In/Sr In/Sr/ In/Sr/ In/Sr/In/Sr/ In/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Cs Sr/Cs/Sr/Cs/ Sr/Cs/ Sr/Cs/ Sr/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaRb/Ga/Tm/Cs Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/Rb/Ga/Tm/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ga/Cs Ga/Cs/Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaK/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/Sr/Zr/ Sr/Zr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Lu/Fe Lu/Fe/Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La La/Dy La/Dy/ La/Dy/ La/Dy/ La/Dy/ La/Dy/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sm/Li/Sr Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/Sm/Li/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/K Mg/K/ Mg/K/Mg/K/ Mg/K/ Mg/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Rb/GaLi/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Li/Cs/Tm Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/Li/Cs/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Zr/K Zr/K/ Zr/K/Zr/K/ Zr/K/ Zr/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Li/Cs Li/Cs/Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Li/K/La Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/ Li/K/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ce/Zr/La Ce/Zr/La/ Ce/Zr/La/Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/ Ca/Al/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Zn/La Sr/Zn/La/ Sr/Zn/La/Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sm/Cs Sm/Cs/ Sm/Cs/ Sm/Cs/Sm/Cs/ Sm/Cs/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La In/K In/K/ In/K/In/K/ In/K/ In/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ho/Cs/Li/LaHo/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs/La/Na Cs/La/Na/ Cs/La/Na/Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/S/Sr La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Lu/TlLu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La K/Cs/Sr/La K/Cs/Sr/La/K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ K/Cs/Sr/La/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/Na/Sr/Lu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Eu/Dy Sr/Eu/Dy/Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Lu/Nb Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ Lu/Nb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/ Sr/Tb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Dy/Gd La/Dy/Gd/ La/Dy/Gd/La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/ Na/Mg/Tl/P/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Pt Na/Pt/ Na/Pt/ Na/Pt/Na/Pt/ Na/Pt/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Gd/Li/K Gd/Li/K/Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/La/Dy/S Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Na/Ce/Co/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Ce Na/Ce/ Na/Ce/Na/Ce/ Na/Ce/ Na/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Na/Ga/Gd/Al/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ba/Rh/TaBa/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCs/Eu/S Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Sm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Sm/Tm/Yb Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaRb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/ Rb/Gd/Li/K/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—Lai/K Ce—La Gd/Ho/Al/P Gd/Ho/Al/P/Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Na/Ca/Lu Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/Na/Ca/Lu/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cu/Sn Cu/Sn/ Cu/Sn/Cu/Sn/ Cu/Sn/ Cu/Sn/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ag/AuAg/Au/ Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Al/Bi Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ Al/Bi/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Al/Mo Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/ Al/Mo/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Al/Nb Al/Nb/ Al/Nb/ Al/Nb/Al/Nb/ Al/Nb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Ce/K Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ Sr/Ce/K/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Au/Pt Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ Au/Pt/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Ga/Bi Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/ Ga/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/W Mg/W/ Mg/W/ Mg/W/ Mg/W/Mg/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Pb/Au Pb/Au/ Pb/Au/Pb/Au/ Pb/Au/ Pb/Au/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sn/MgSn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/ Sr/Ta/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Na Na/ Na/ Na/ Na/ Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr Sr/ Sr/ Sr/ Sr/ Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca Ca/ Ca/ Ca/ Ca/ Ca/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Yb Yb/ Yb/ Yb/ Yb/ Yb/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Cs Cs/ Cs/ Cs/ Cs/ Cs/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sb Sb/ Sb/ Sb/ Sb/ Sb/La_(3.8)Nd_(0.2)O₆/ Y—La/ Zr—La/ Pr—La/ Ce—La/ Zn/Bi Zn/Bi Zn/Bi Zn/BiZn/Bi Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ Gd/Ho/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La Zr/Bi Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/ Zr/Bi/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ho/Sr Ho/Sr/ Ho/Sr/ Ho/Sr/Ho/Sr/ Ho/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Gd/Ho/SrGd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaNa/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Na/Zr/Eu/Tm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Ho/Tm/NaSr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/Sr/Pb/ Sr/Pb/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/W/Li Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ Sr/W/Li/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/Sr/Hf/ Sr/Hf/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Au/Re Au/Re/Au/Re/ Au/Re/ Au/Re/ Au/Re/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaSr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/ Sr/W/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La La/Nd La/Nd/ La/Nd/ La/Nd/ La/Nd/ La/Nd/ La_(3.8)Nd_(0.2)O₆ Y—LaZr—La Pr—La Ce—La La/Sm La/Sm/ La/Sm/ La/Sm/ La/Sm/ La/Sm/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Ce La/Ce/ La/Ce/ La/Ce/La/Ce/ La/Ce/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Sr La/Sr/La/Sr/ La/Sr/ La/Sr/ La/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Bi/Sr La/Bi/Sr/ La/Bi/Sr/La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaLa/Ce/Nd/Sr La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La La/Bi/Ce/Nd/SrLa/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/Gd Eu/Gd/Eu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaCa/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/ Eu/Sr/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Mg/Sr Mg/Sr/ Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ce/Mg/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaGd/Sm Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ La_(3.8)Nd_(0.2)O₆Y—La Zr—La Pr—La Ce—La Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/S Rb/S/ Rb/S/ Rb/S/ Rb/S/Rb/S/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Sr/Nd Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ Sr/Nd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Eu/YEu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ Eu/Y/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—LaMg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—LaPr—La Ce—La La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/ La/Mg/ La_(3.8)Nd_(0.2)O₆N Y—La Zr—La Pr—La Ce—La Mg/Nd/Fe Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—La Ce—La Rb/SrRb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ La_(3.8)Nd_(0.2)O₆ Y—La Zr—La Pr—LaCe—La

TABLE 12 NANOWIRES (NW) DOPED WITH SPECIFIC DOPANTS (DOP) Dop\NWLn1_(4−x)Ln2_(x)O₆* La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Na Eu/Na/ Eu/Na/Eu/Na/ Eu/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Na Sr/Na/Sr/Na/ Sr/Na/ Sr/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Zr/Eu/Ca Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/ Na/Zr/Eu/Ca/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Na Mg/Na/ Mg/Na/ Mg/Na/Mg/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Sm/Ho/TmSr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Sr/Sm/Ho/Tm/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/ Sr/W/ Sr/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/La/K Mg/La/K/ Mg/La/K/Mg/La/K/ Mg/La/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/K/Mg/Tm Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/ Na/K/Mg/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Dy/K Na/Dy/K/ Na/Dy/K/Na/Dy/K/ Na/Dy/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/DyNa/La/Dy/ Na/La/Dy/ Na/La/Dy/ Na/La/Dy/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Eu Na/La/Eu/ Na/La/Eu/ Na/La/Eu/Na/La/Eu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Eu/InNa/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Na/La/Eu/In/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/K Na/La/K/ Na/La/K/ Na/La/K/ Na/La/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/La/Li/Cs Na/La/Li/Cs/Na/La/Li/Cs/ Na/La/Li/Cs/ Na/La/Li/Cs/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La K/La/ K/La/ K/La/ K/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/S K/La/S/ K/La/S/K/La/S/ K/La/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/Na K/Na/K/Na/ K/Na/ K/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/CsLi/Cs/ Li/Cs/ Li/Cs/ Li/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Cs/La Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Li/Cs/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs/La/Tm Li/Cs/La/Tm/ Li/Cs/La/Tm/Li/Cs/La/Tm/ Li/Cs/La/Tm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLi/Cs/Sr/Tm Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/ Li/Cs/Sr/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Sr/Cs Li/Sr/Cs/Li/Sr/Cs/ Li/Sr/Cs/ Li/Sr/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Sr/Zn/K Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/ Li/Sr/Zn/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Ga/Cs Li/Ga/Cs/Li/Ga/Cs/ Li/Ga/Cs/ Li/Ga/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/K/Sr/La Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/ Li/K/Sr/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na Li/Na/ Li/Na/ Li/Na/Li/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na/Rb/GaLi/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Li/Na/Rb/Ga/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zr Sr/Zr/ Sr/Zr/ Sr/Zr/ Sr/Zr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Na/Sr Li/Na/Sr/Li/Na/Sr/ Li/Na/Sr/ Li/Na/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Na/Sr/La Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/ Li/Na/Sr/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Sm/Cs Li/Sm/Cs/Li/Sm/Cs/ Li/Sm/Cs/ Li/Sm/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ba/Sm/Yb/S Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/ Ba/Sm/Yb/S/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ba/Tm/K/La Ba/Tm/K/La/Ba/Tm/K/La/ Ba/Tm/K/La/ Ba/Tm/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Ba/Tm/Zn/K Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/ Ba/Tm/Zn/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/K/La Cs/K/La/ Cs/K/La/Cs/K/La/ Cs/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOCs/La/Tm/Na Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/ Cs/La/Tm/Na/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/Li/K/La Cs/Li/K/La/Cs/Li/K/La/ Cs/Li/K/La/ Cs/Li/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sm/Li/Sr/Cs Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/ Sm/Li/Sr/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs/La Sr/Cs/La/Sr/Cs/La/ Sr/Cs/La/ Sr/Cs/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sr/Tm/Li/Cs Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/ Sr/Tm/Li/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/K Zn/K/ Zn/K/ Zn/K/Zn/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Cs/K/LaZr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Zr/Cs/K/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ca/In/Ni Rb/Ca/In/Ni/ Rb/Ca/In/Ni/Rb/Ca/In/Ni/ Rb/Ca/In/Ni/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSr/Ho/Tm Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Sr/Ho/Tm/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd/S La/Nd/S/ La/Nd/S/ La/Nd/S/ La/Nd/S/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tb Sr/Tb/ Sr/Tb/ Sr/Tb/Sr/Tb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Rb/Ca Li/Rb/Ca/Li/Rb/Ca/ Li/Rb/Ca/ Li/Rb/Ca/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/K Li/K/ Li/K/ Li/K/ Li/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Tm/Lu/Ta/P Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/ Tm/Lu/Ta/P/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ca/Dy/P Rb/Ca/Dy/P/Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Rb/Ca/Dy/P/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Mg/La/Yb/Zn Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/ Mg/La/Yb/Zn/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Sr/Lu Rb/Sr/Lu/Rb/Sr/Lu/ Rb/Sr/Lu/ Rb/Sr/Lu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Na/Sr/Lu/Nb Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/ Na/Sr/Lu/Nb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Eu/Hf Na/Eu/Hf/Na/Eu/Hf/ Na/Eu/Hf/ Na/Eu/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Dy/Rb/Gd Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Dy/Rb/Gd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Pt/Bi Na/Pt/Bi/ Na/Pt/Bi/ Na/Pt/Bi/Na/Pt/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Hf Rb/Hf/Rb/Hf/ Rb/Hf/ Rb/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/CsCa/Cs/ Ca/Cs/ Ca/Cs/ Ca/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ca/Mg/Na Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ca/Mg/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Hf/Bi Hf/Bi/ Hf/Bi/ Hf/Bi/ Hf/Bi/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Sn Sr/Sn/ Sr/Sn/ Sr/Sn/Sr/Sn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/Sr/W/ Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Nb Sr/Nb/Sr/Nb/ Sr/Nb/ Sr/Nb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/WZr/W/ Zr/W/ Zr/W/ Zr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOY/W Y/W/ Y/W/ Y/W/ Y/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/W Na/W/ Na/W/ Na/W/ Na/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sr/Ce Sr/Ce/ Sr/Ce/ Sr/Ce/ Sr/Ce/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/W Bi/W/ Bi/W/ Bi/W/ Bi/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Cs Bi/Cs/ Bi/Cs/ Bi/Cs/Bi/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Ca Bi/Ca/ Bi/Ca/Bi/Ca/ Bi/Ca/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Sn Bi/Sn/Bi/Sn/ Bi/Sn/ Bi/Sn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/SbBi/Sb/ Bi/Sb/ Bi/Sb/ Bi/Sb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ge/Hf Ge/Hf/ Ge/Hf/ Ge/Hf/ Ge/Hf/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Hf/Sm Hf/Sm/ Hf/Sm/ Hf/Sm/ Hf/Sm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Ag Sb/Ag/ Sb/Ag/ Sb/Ag/Sb/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Bi Sb/Bi/ Sb/Bi/Sb/Bi/ Sb/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Au Sb/Au/Sb/Au/ Sb/Au/ Sb/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/SmSb/Sm/ Sb/Sm/ Sb/Sm/ Sb/Sm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sb/Sr Sb/Sr/ Sb/Sr/ Sb/Sr/ Sb/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/W Sb/W/ Sb/W/ Sb/W/ Sb/W/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Hf Sb/Hf/ Sb/Hf/ Sb/Hf/Sb/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb/Yb Sb/Yb/ Sb/Yb/Sb/Yb/ Sb/Yb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Pr/KSr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Sr/Pr/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sb/Sn Sb/Sn/ Sb/Sn/ Sb/Sn/ Sb/Sn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Au Yb/Au/ Yb/Au/ Yb/Au/ Yb/Au/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Ta Yb/Ta/ Yb/Ta/ Yb/Ta/Yb/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/W Yb/W/ Yb/W/Yb/W/ Yb/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/Sr Yb/Sr/Yb/Sr/ Yb/Sr/ Yb/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb/PbYb/Pb/ Yb/Pb/ Yb/Pb/ Yb/Pb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Yb/W Yb/W/ Yb/W/ Yb/W/ Yb/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Yb/Ag Yb/Ag/ Yb/Ag/ Yb/Ag/ Yb/Ag/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Sr Au/Sr/ Au/Sr/ Au/Sr/ Au/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO W/Ge W/Ge/ W/Ge/ W/Ge/W/Ge/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ta/Sr Ta/Sr/ Ta/Sr/Ta/Sr/ Ta/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ta/Hf Ta/Hf/Ta/Hf/ Ta/Hf/ Ta/Hf/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO W/AuW/Au/ W/Au/ W/Au/ W/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOCa/W Ca/W/ Ca/W/ Ca/W/ Ca/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Li Sm/Li/ Sm/Li/ Sm/Li/ Sm/Li/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/K La/K/ La/K/ La/K/La/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/Cs Zn/Cs/ Zn/Cs/Zn/Cs/ Zn/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zr/KSr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Sr/Zr/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Na/K/Mg Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Na/K/Mg/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Cs Zr/Cs/ Zr/Cs/ Zr/Cs/ Zr/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Ce Ca/Ce/ Ca/Ce/ Ca/Ce/Ca/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Li/Cs Na/Li/Cs/Na/Li/Cs/ Na/Li/Cs/ Na/Li/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Li/Sr Li/Sr/ Li/Sr/ Li/Sr/ Li/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Dy/K La/Dy/K/ La/Dy/K/ La/Dy/K/ La/Dy/K/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Dy/K Dy/K/ Dy/K/ Dy/K/Dy/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Mg La/Mg/ La/Mg/La/Mg/ La/Mg/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Nd/In/KNa/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Na/Nd/In/K/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO In/Sr In/Sr/ In/Sr/ In/Sr/ In/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs Sr/Cs/ Sr/Cs/ Sr/Cs/Sr/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Ga/Tm/CsRb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Rb/Ga/Tm/Cs/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ga/Cs Ga/Cs/ Ga/Cs/ Ga/Cs/ Ga/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/Zr/Ag K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ K/La/Zr/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Lu/Fe Lu/Fe/ Lu/Fe/ Lu/Fe/ Lu/Fe/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tm Sr/Tm/ Sr/Tm/ Sr/Tm/ Sr/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Dy La/Dy/ La/Dy/ La/Dy/La/Dy/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Li/Sr Sm/Li/Sr/Sm/Li/Sr/ Sm/Li/Sr/ Sm/Li/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Mg/K Mg/K/ Mg/K/ Mg/K/ Mg/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Li/Rb/Ga Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/ Li/Rb/Ga/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ce/K Sr/Ce/K/ Sr/Ce/K/Sr/Ce/K/ Sr/Ce/K/ Ln1⁴⁻Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs/TmLi/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Li/Cs/Tm/ Ln1⁴⁻Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Zr/K Zr/K/ Zr/K/ Zr/K/ Zr/K/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/Cs Li/Cs/ Li/Cs/ Li/Cs/ Li/Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Li/K/La Li/K/La/ Li/K/La/Li/K/La/ Li/K/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ce/Zr/LaCe/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ce/Zr/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Al/La Ca/Al/La/ Ca/Al/La/ Ca/Al/La/Ca/Al/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Zn/LaSr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Sr/Zn/La/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Cs/Zn Sr/Cs/Zn/ Sr/Cs/Zn/ Sr/Cs/Zn/Sr/Cs/Zn/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Cs Sm/Cs/Sm/Cs/ Sm/Cs/ Sm/Cs/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO In/KIn/K/ In/K/ In/K/ In/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSr/Pr Sr/Pr/ Sr/Pr/ Sr/Pr/ Sr/Pr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Ho/Cs/Li/La Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/ Ho/Cs/Li/La/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/La/Na Cs/La/Na/Cs/La/Na/ Cs/La/Na/ Cs/La/Na/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO La/S/Sr La/S/Sr/ La/S/Sr/ La/S/Sr/ La/S/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/La/Zr/Ag K/La/Zr/Ag/ K/La/Zr/Ag/K/La/Zr/Ag/ K/La/Zr/Ag/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLu/Tl Lu/Tl/ Lu/Tl/ Lu/Tl/ Lu/Tl/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Pr/Zn Pr/Zn/ Pr/Zn/ Pr/Zn/ Pr/Zn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Sr/La Rb/Sr/La/ Rb/Sr/La/ Rb/Sr/La/Rb/Sr/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Sr/Eu/CaNa/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Na/Sr/Eu/Ca/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO K/Cs/Sr/La K/Cs/Sr/La/ K/Cs/Sr/La/K/Cs/Sr/La/ K/Cs/Sr/La/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Sr/Lu Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Na/Sr/Lu/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Eu/Dy Sr/Eu/Dy/ Sr/Eu/Dy/ Sr/Eu/Dy/Sr/Eu/Dy/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Lu/Nb Lu/Nb/Lu/Nb/ Lu/Nb/ Lu/Nb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLa/Dy/Gd La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ La/Dy/Gd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Mg/Tl/P Na/Mg/Tl/P/ Na/Mg/Tl/P/Na/Mg/Tl/P/ Na/Mg/Tl/P/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Pt Na/Pt/ Na/Pt/ Na/Pt/ Na/Pt/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Gd/Li/K Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Gd/Li/K/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/K/Lu Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/ Rb/K/Lu/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/La/Dy/S Sr/La/Dy/S/Sr/La/Dy/S/ Sr/La/Dy/S/ Sr/La/Dy/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Na/Ce/Co Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/ Na/Ce/Co/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Ce Na/Ce/ Na/Ce/ Na/Ce/Na/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Tb/K Sr/Tb/K/Sr/Tb/K/ Sr/Tb/K/ Sr/Tb/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Ga/Gd/Al Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/ Na/Ga/Gd/Al/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ba/Rh/Ta Ba/Rh/Ta/Ba/Rh/Ta/ Ba/Rh/Ta/ Ba/Rh/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ba/Ta Ba/Ta/ Ba/Ta/ Ba/Ta/ Ba/Ta/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Al/Bi Na/Al/Bi/ Na/Al/Bi/ Na/Al/Bi/Na/Al/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs/Eu/S Cs/Eu/S/Cs/Eu/S/ Cs/Eu/S/ Cs/Eu/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOSm/Tm/Yb/Fe Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/ Sm/Tm/Yb/Fe/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sm/Tm/Yb Sm/Tm/Yb/Sm/Tm/Yb/ Sm/Tm/Yb/ Sm/Tm/Yb/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Hf/Zr/Ta Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Hf/Zr/Ta/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/Gd/Li/K Rb/Gd/Li/K/ Rb/Gd/Li/K/Rb/Gd/Li/K/ Rb/Gd/Li/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOGd/Ho/Al/P Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/ Gd/Ho/Al/P/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na/Ca/Lu Na/Ca/Lu/Na/Ca/Lu/ Na/Ca/Lu/ Na/Ca/Lu/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Cu/Sn Cu/Sn/ Cu/Sn/ Cu/Sn/ Cu/Sn/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ag/Au Ag/Au/ Ag/Au/ Ag/Au/ Ag/Au/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Bi Al/Bi/ Al/Bi/ Al/Bi/Al/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Mo Al/Mo/ Al/Mo/Al/Mo/ Al/Mo/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Hf/RbSr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Sr/Hf/Rb/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Al/Nb Al/Nb/ Al/Nb/ Al/Nb/ Al/Nb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Pt Au/Pt/ Au/Pt/ Au/Pt/Au/Pt/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ga/Bi Ga/Bi/ Ga/Bi/Ga/Bi/ Ga/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/W Mg/W/Mg/W/ Mg/W/ Mg/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Pb/AuPb/Au/ Pb/Au/ Pb/Au/ Pb/Au/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Sn/Mg Sn/Mg/ Sn/Mg/ Sn/Mg/ Sn/Mg/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zn/Bi Zn/Bi/ Zn/Bi/ Zn/Bi/ Zn/Bi/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ta Sr/Ta/ Sr/Ta/ Sr/Ta/Sr/Ta/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Na Na/ Na/ Na/ Na/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr Sr/ Sr/ Sr/ Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca Ca/ Ca/ Ca/ Ca/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Yb Yb/ Yb/ Yb/ Yb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Cs Cs/ Cs/ Cs/ Cs/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sb Sb/ Sb/ Sb/ Sb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Gd/Ho Gd/Ho/ Gd/Ho/ Gd/Ho/Gd/Ho/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Zr/Bi Zr/Bi/ Zr/Bi/Zr/Bi/ Zr/Bi/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ho/Sr Ho/Sr/Ho/Sr/ Ho/Sr/ Ho/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/BSr/B/ Sr/B/ Sr/B/ Sr/B/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOGd/Ho/Sr Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Gd/Ho/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr Ca/Sr/ Ca/Sr/ Ca/Sr/ Ca/Sr/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr/W Ca/Sr/W/ Ca/Sr/W/Ca/Sr/W/ Ca/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgONa/Zr/Eu/Tm Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/ Na/Zr/Eu/Tm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Ho/Tm/Na Sr/Ho/Tm/Na/Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Sr/Ho/Tm/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Pb Sr/Pb/ Sr/Pb/ Sr/Pb/ Sr/Pb/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W/Li Sr/W/Li/ Sr/W/Li/Sr/W/Li/ Sr/W/Li/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ca/Sr/WCa/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ca/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Sr/Hf Sr/Hf/ Sr/Hf/ Sr/Hf/ Sr/Hf/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Au/Re Au/Re/ Au/Re/ Au/Re/ Au/Re/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/W Sr/W/ Sr/W/ Sr/W/Sr/W/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd La/Nd/ La/Nd/La/Nd/ La/Nd/ Ln1⁴⁻Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Sm La/Sm/La/Sm/ La/Sm/ La/Sm/ Ln1⁴⁻Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/CeLa/Ce/ La/Ce/ La/Ce/ La/Ce/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO La/Sr La/Sr/ La/Sr/ La/Sr/ La/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Nd/Sr La/Nd/Sr/ La/Nd/Sr/ La/Nd/Sr/La/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Bi/SrLa/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ La/Bi/Sr/ L Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Ce/Nd/Sr La/Ce/Nd/Sr/ La/Ce/Nd/Sr/La/Ce/Nd/Sr/ La/Ce/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgOLa/Bi/Ce/Nd/Sr La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/ La/Bi/Ce/Nd/Sr/La/Bi/Ce/Nd/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/GdEu/Gd/ Eu/Gd/ Eu/Gd/ Eu/Gd/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Ca/Na Ca/Na/ Ca/Na/ Ca/Na/ Ca/Na/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Sm Eu/Sm/ Eu/Sm/ Eu/Sm/ Eu/Sm/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Sr Eu/Sr/ Eu/Sr/ Eu/Sr/Eu/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Sr Mg/Sr/ Mg/Sr/Mg/Sr/ Mg/Sr/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Ce/Mg Ce/Mg/Ce/Mg/ Ce/Mg/ Ce/Mg/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Gd/SmGd/Sm/ Gd/Sm/ Gd/Sm/ Gd/Sm/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Au/Pb Au/Pb/ Au/Pb/ Au/Pb/ Au/Pb/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Bi/Hf Bi/Hf/ Bi/Hf/ Bi/Hf/ Bi/Hf/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Rb/S Rb/S/ Rb/S/ Rb/S/Rb/S/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Nd Sr/Nd/ Sr/Nd/Sr/Nd/ Sr/Nd/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Eu/Y Eu/Y/Eu/Y/ Eu/Y/ Eu/Y/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Sr/Hf/KSr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Sr/Hf/K/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆Y₂O₃ MgO Mg/Nd Mg/Nd/ Mg/Nd/ Mg/Nd/ Mg/Nd/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO La/Mg La/Mg/ La/Mg/ La/Mg/ La/Mg/Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO Mg/Nd/Fe Mg/Nd/Fe/Mg/Nd/Fe/ Mg/Nd/Fe/ Mg/Nd/Fe/ Ln1_(4−x)Ln2_(x)O₆ La_(4−x)Ln1_(x)O₆ Y₂O₃MgO Rb/Sr Rb/Sr/ Rb/Sr/ Rb/Sr/ Rb/Sr/ Ln1_(4−x)Ln2_(x)O₆La_(4−x)Ln1_(x)O₆ Y₂O₃ MgO *Ln1 and Ln2 are each independently alanthanide element, wherein Ln1 and Ln2 are not the same and x is anumber ranging from greater than 0 to less than 4

As used in Tables 1-12 and throughout the specification, a nanowirecomposition represented by E¹/E²/E³ etc., wherein E¹, E² and E³ are eachindependently an element or a compound comprising one or more elements,refers to a nanowire composition comprised of a mixture of E¹, E² andE³. E¹/E²/E³, etc. are not necessarily present in equal amounts and neednot form a bond with one another. For example, a nanowire comprisingLi/MgO refers to a nanowire comprising Li and MgO, for example, Li/MgOmay refer to a MgO nanowire doped with Li. By way of another example, ananowire comprising NaMnO₄/MgO refers to a nanowire comprised of amixture of NaMnO₄ and MgO. Dopants may be added in suitable form. Forexample in a lithium doped magnesium oxide nanowire (Li/MgO), the Lidopant can be incorporated in the form of Li₂O, Li₂CO₃, LiOH, or othersuitable forms. Li may be fully incorporated in the MgO crystal lattice(e.g., (Li,Mg)O) as well. Dopants for other nanowires may beincorporated analogously.

In some more specific embodiments, the dopant is selected from Li, Baand Sr. In other specific embodiments, the nanowires comprise Li/MgO,Ba/MgO, Sr/La₂O₃, Ba/La₂O₃, Mn/Na₂WO₄, Mn₂O₃/Na₂WO₄, Mn₃O₄/Na₂WO₄,Mg₆MnO₈, Li/B/Mg₆MnO₈, Na/B/Mg₆MnO₈, Zr₂Mo₂O₈ or NaMnO₄/MgO.

In some other specific embodiments, the nanowire comprises a mixed oxideof Mn and Mg with or without B and with or without Li. Additionaldopants for such nanowires may comprise doping elements selected fromGroup 1 and 2 and groups 7-13. The dopants may be present as singledopants or in combination with other dopants. In certain specificembodiments of nanowires comprising a mixed oxide of Mn and Mg with orwithout B and with or without Li., the dopant comprises a combination ofelements from group 1 and group 8-11.

Nanowires comprising mixed oxides of Mn and Mg are well suited forincorporation of dopants because magnesium atoms can be easilysubstituted by other atoms as long as their size is comparable withmagnesium. A family of “doped” Mg₆MnO₈ compounds with the compositionM_((x))Mg_((6-x))MnO₈, wherein each M is independently a dopant asdefined herein and x is 0 to 6, can thus be created. The oxidation stateof Mn can be tuned by selecting different amounts (i.e., differentvalues of x) of M with different oxidation states, for exampleLi_((x))Mg_((6-x))MnO₈ would contain a mixture of Mn(IV) and Mn(V) withx<1 and a mixture that may include Mn(V), Mn(VI), Mn(VII) with x>1. Themaximum value of x depends on the ability of a particular atom M to beincorporated in the Mg₆MnO₈ crystal structure and therefore variesdepending on M. It is believed that the ability to tune the manganeseoxidation state as described above could have advantageous effect on thecatalytic activity of the disclosed nanowires.

Examples of nanowires comprising Li/Mn/Mg/B and an additional dopantinclude; Li/Mn/Mg/B doped with Co; Li/Mn/Mg/B doped with Na, Li/Mn/Mg/Bdoped with Be; Li/Mn/Mg/B doped with Al; Li/Mn/Mg/B doped with Hf;Li/Mn/Mg/B doped with Zr; Li/Mn/Mg/B doped with Zn; Li/Mn/Mg/B dopedwith Rh and Li/Mn/Mg/B doped with Ga. Nanowires comprising Li/Mn/Mg/Bdoped with different combinations of these dopants are also provided.For example, in some embodiments the Li/Mn/Mg/B nanowires are doped withNa and Co. In other embodiments, the Li/Mn/Mg/B nanowires are doped withGa and Na.

In other embodiments, nanowires comprising Mn/W with or without dopantsare provided. For example, the present inventors have found through highthroughput testing that nanowires comprising Mn/W and various dopantsare good catalysts in the OCM reaction. Accordingly, in someembodiments, the Mn/W nanowires are doped with Ba. In other embodiments,the Mn/W nanowires are doped with Be. In yet other embodiments, the Mn/Wnanowires are doped with Te.

In any of the above embodiments, the Mn/W nanowires may comprise a SiO₂support. Alternatively, the use of different supports such as ZrO₂, HfO₂and In₂O₃ in any of the above embodiments has been shown to promote OCMactivity at reduced temperature compared to the same catalyst supportedon silica with limited reduction in selectivity.

Nanowires comprising rare earth oxides doped with various elements arealso effective catalysts in the OCM reaction. In certain specificembodiments, the rare earth oxide or oxy-hydroxide can be any rareearth, preferably La, Nd, Eu, Sm, Yb, Gd. In certain embodiments of thenanowires comprising rare earth elements or yttria, the dopant comprisesalkali earth (group 2) elements. The degree of effectiveness of aparticular dopant is a function of the rare earth used and theconcentration of the alkali earth dopant. In addition to Alkali earthelements, further embodiments of the rare earth or yttria nanowiresinclude embodiments wherein the nanowires comprise alkali elements asdopants, which further promote the selectivity of the OCM catalyticactivity of the doped material. In yet other embodiments of theforegoing, the nanowires comprise both an alkali element and alkaliearth element as dopant. In still further embodiments, an additionaldopant can be selected from an additional rare earth and groups 3, 4, 8,9, 10, 13, 14.

The foregoing rare earth catalyst may be doped prior to, or afterformation of the rare earth oxide. In one embodiment, the correspondingrare earth salt is mixed with the corresponding dopant salt to form asolution or a slurry which is dried and then calcined in a range of 400°C. to 900° C., or between 500° C. and 700° C. In another embodiment, therare earth oxide is formed first through calcination of a rare earthsalt and then contacted with a solution comprising the doping elementprior to drying and calcination between 300° C. and 800° C., or between400° C. and 700° C.

In other embodiments, the nanowires comprise La₂O₃ or LaO_(y)(OH)_(x),wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, dopedwith Na, Mg, Ca, Sr, Ga, Sc, Y, Zr, In, Nd, Eu, Sm, Ce, Gd orcombinations thereof. In yet further embodiments, the La₂O₃ orLaO_(y)(OH)_(x) nanowires are doped with binary dopant combinations, forexample Eu/Na; Eu/Gd; Ca/Na; Eu/Sm; Eu/Sr; Mg/Sr; Ce/Mg; Gd/Sm, Mg/Na,Mg/Y, Ga/Sr, Nd/Mg, Gd/Na or Sm/Na. In some other embodiments, the La₂O₃or LaO_(y)(OH)_(x) nanowires are doped with a ternary dopantcombination, for example Ca—Mg—Na.

In other embodiments, the nanowires comprise Nd₂O₃ or NdO_(y)(OH)_(x),wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, dopedwith Sr, Ca, Rb, Li, Na or combinations thereof. In certain otherembodiments, the Nd₂O₃ or NdO_(y)(OH)_(x) nanowires are doped withbinary dopant combinations, for example Ca/Sr, Rb/Sr, Ta/Sr or Al/Sr.

In still other examples of doped nanowires, the nanowires comprise Yb₂O₃or YbO_(y)(OH)_(x), wherein y ranges from 0 to 1.5, x ranges from 0 to 3and 2y+x=3, doped with Sr, Ca, Ba, Nd or combinations thereof. Incertain other embodiments, the Yb₂O₃ or YbO_(y)(OH)_(x) OCM nanowiresare doped with a binary combination, for example of Sr/Nd.

Still other examples of doped nanowires Eu₂O₃ or EuO_(y)(OH)_(x)nanowires, wherein y ranges from 0 to 1.5, x ranges from 0 to 3 and2y+x=3, doped with Sr, Ba, Sm, Gd, Na or combinations thereof or abinary dopant combination, for example Sr/Na or Sm/Na.

Example of dopants for Sm₂O₃ or SmO_(y)(OH)_(x) nanowires, wherein x andy are each independently an integer from 1 to 10, include Sr, andexamples of dopants for Y₂O₃ or YO_(y)(OH)_(x) nanowires, wherein yranges from 0 to 1.5, x ranges from 0 to 3 and 2y+x=3, comprise Ga, La,Nd or combinations thereof. In certain other embodiments, the Y₂O₃ orYO_(y)(OH)_(x) nanowires comprise a binary dopant combination, forexample Sr/Nd, Eu/Y or Mg/Nd or a tertiary dopant combination, forexample Mg/Nd/Fe.

In yet other embodiments, the nanowires comprise Ln₂O₃ orLn_(z)O_(y)(OH)_(x), wherein Ln is at each occurrence, independently alanthanide, x ranges from 0 to 3 and 2y+x=3, y ranges from 0 to 1.5, andz is 1, 2 or 3, and the nanowires are doped with Li, Na, K, Rb, Cs, Mg,Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,Lu, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Ni, Pd, Pt, Cu, Ag, Au, Zn, Al,Ga, In, Tl, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te or combinationsthereof. In certain other embodiments, the Ln₂O₃ or Ln_(z)O_(y)(OH)_(x)nanowires comprise only one dopant, for example Sr, a binary dopantcombination, for example Na/Mg, Na/Sr, Mg/Sr, Li/Cs, Sr/W, Hf/Bi, Na/Eu,Zn/K, Sb/Ag, Sr/Ta, a tertiary dopant combination, for example Li/Na/Sr,Na/La/Eu, Li/Sr/Cs, Dy/Rb/Gd, Mg/La/K, or a quaternary dopantcombination, for example Na/Zr/Eu/Ca, Na/La/Eu/In, Na/K/Mg/Tm,Li/Cs/Sr/Tm, Ba/Tm/Zn/K, Mg/La/Yb/Zn.

Rare earth nanowires, which without doping often have low OCMselectivity, can be greatly improved by doping to reduce theircombustion activity. In particular, nanowires comprising CeO₂ and Pr₂O₃tend to have strong total oxidation activity for methane, however dopingwith additional rare earth elements can significantly moderate thecombustion activity and improve the overall utility of the catalyst.Example of dopants for improving the selectivity for Pr₂O₃ orPrO_(y)(OH)_(x) nanowires, wherein y ranges from 0 to 1.5, x ranges from0 to 3 and 2y+x=3, comprise binary dopants, for example Nd/Mg, La/Mg orYb/Sr.

In some embodiments, dopants are present in the nanowires in, forexample, less than 50 at %, less than 25 at %, less than 10 at %, lessthan 5 at % or less than 1 at %.

In other embodiments of the nanowires, the atomic ratio (w/w) of the oneor more metal elements selected from Groups 1-7 and lanthanides andactinides in the form of an oxide and the dopant ranges from 1:1 to10,000:1, 1:1 to 1,000:1 or 1:1 to 500:1.

In further embodiments, the nanowires comprise one or more metalelements from Group 2 in the form of an oxide and a dopant from Group 1.In further embodiments, the nanowires comprise magnesium and lithium. Inother embodiments, the nanowires comprise one or more metal elementsfrom Group 2 and a dopant from Group 2, for example, in someembodiments, the nanowires comprise magnesium oxide and barium. In otherembodiments, the nanowires comprise one or more metal elements fromGroup 2, a dopant from Group 2 and an additional dopant, for example, insome embodiments, the nanowires comprise magnesium oxide and are dopedwith strontium and tungsten dopants (i.e., Sr/W/MgO). In anotherembodiment, the nanowires comprise an element from the lanthanides inthe form of an oxide and a dopant from Group 1 or Group 2. In furtherembodiments, the nanowires comprise lanthanum and strontium.

Various methods for preparing doped nanowires are provided. In oneembodiment, the doped nanowires can be prepared by co-precipitating ananowire metal oxide precursor and a dopant precursor. In theseembodiments, the doping element may be directly incorporated into thenanowire.

Template Directed Synthesis of Nanowires

In some embodiments, the nanowires can be prepared in a solution phaseusing an appropriate template. In this context, an appropriate templatecan be any synthetic or natural material, or combination thereof, thatprovides nucleation sites for binding ions (e.g. metal element ionsand/or hydroxide or other anions) and causing the growth of a nanowire.The templates can be selected such that certain control of thenucleation sites, in terms of their composition, quantity and locationcan be achieved in a statistically significant manner. The templates aretypically linear or anisotropic in shape, thus directing the growth of ananowire.

In contrast to other template directed preparation of nanostructures,the nanowires of the invention are generally not prepared fromnanoparticles deposited on a template in a reduced state which are thenheat treated and fused into an elongated nanoporous nanostructure. Inparticular, such methods are not generally applicable to continuousnanowires comprising one or more elements from any of Groups 1 through7, lanthanides, actinides or combinations thereof. Instead of forming aplurality of catalyst nanoparticles, nanocrystals, or nanocrystalliteson the surface of the template (e.g., phage), the nanowires of theinvention are preferably prepared by nucleation of an oxidized metalelement (e.g., in the form of a metal ion) and subsequent growth of ananowire. After nucleation of the oxidized metal element, the nanowiresare generally calcined to produce the desired oxide, but annealing ofnanoparticles is not necessary to form the nanowires.

Accordingly, the nanowires used in the context of the invention have anumber of properties that differentiate them from other nanostructures,such as those created as fused aggregates of nanoparticles. Inparticular, the nanowires are characterized as having one or more of; asubstantially non-nanoporous structure, an average crystal domain size,either before and/or after calcination, of greater than 5 nm, and ananisotropic crystal habit.

In the context of non-nanoporous nanowires, preferred compositions aredistinguished from elongated nanostructures formed as nanoporousaggregates of nanoparticles by virtue of their substantiallynon-nanoporous structures. Such substantially non-nanoporous nanowirestructures will preferably have a surface area of less than 150 m²/g,more preferably less than 100 m²/g, less than 50 m²/g, less than 40m²/g, less than 30 m²/g less than 25 m²/g, less than 20 m²/g, less than15 m²/g, less than 10 m²/g, or between 1 m²/g and any of the foregoing.As will be appreciated, nanowires created through templating processes,where additional aggregates may fuse to a non-nanoporous orsubstantially non-nanoporous nanowire core, will typically have highersurface areas, e.g., surface areas toward the higher end of the range,while nanowires created from other processes, e.g., by hydrothermalprocesses, will typically have lower surface areas.

In certain aspects, the nanowires of the invention are characterized byrelatively large crystal domain sizes in the context of relatively highsurface area nanowire structures. In particular, and as notedpreviously, for those nanowires of the invention having an averagecrystal domain size in at least one crystal dimension that is greaterthan 5 nm, preferred nanowires of the invention will typically have anaverage crystal domain size in at least one crystal dimension that isgreater than 10 nm, and in more preferred aspects, greater than 20 nm.

In certain embodiments, the nanowires of the invention may also becharacterized by additional structural properties. For example, incertain aspects, the nanowires of the invention may be characterized bya continuous crystal structure within the nanowire, excluding stackingfaults. In certain aspects, the nanowires of the invention may becharacterized by an aligned crystal structure within the nanowireconsisting of parallel, aligned crystal domains.

In some embodiments, methods for forming nanowires having the empiricalformula M4_(w)M5_(x)M6_(y)O_(z) are provided, wherein M4 comprises oneor more elements selected from Groups 1 through 4, M5 comprises one ormore elements selected from Group 7 and M6 comprises one or moreelements selected from Groups 5 through 8 and Groups 14 through 15 andw, x, y and z are integers such that the overall charge is balanced. Themethods comprise combining one or more sources of M4, one or moresources of M5, and one or more sources of M6 in the presence of atemplating agent and a solvent to form a mixture.

In certain embodiments, M4 includes one or more elements selected fromGroup 1, such as Na, while M6 includes one or more elements selectedfrom Group 6, such as W and M3 is Mn. In one embodiment, M4 is Na andthe source of M4 is NaCl, M5 is Mn and the source of M5 is Mn(NO₃)₂, M6is W and the source of M6 is WO₃, the solvent is water, and thetemplating agent is a bacteriophage.

In various embodiments, the source of M4 can be one or more of achloride, bromide, iodide, oxychloride, oxybromide, oxyiodide, nitrate,oxynitrate, sulfate or phosphate salt of any of Group 1, Group 2, Group3, or a Group 4 element. In an embodiment, sources of M4 include LiCl,KCl, MgCl₂, CaCl₂, ScCl₃, TiCl₄, KBr, CaBr₂, Sc(NO₃)₃, Y(NO₃)₃, TiBr₄,ZrBr₄, Zr(NO₃)₄, ZrOCl₂, ZrO(NO₃)₂, Na₂SO₄, and Zr(SO₄)₂. For any givensource of M4, a source of M6 can be one or more of an oxide, oxide salt,or an oxyacid of any of Group 5, Group 6, Group 7, Group 8, Group 14 andGroup 15 elements. In an embodiment, sources of M6 include MoO₃,(NH₄)₆Mo₇O₂₄, WO₃, Na₂WO₄, H₂WO₄, CO₂O₃, P₂O₅, H₃PO₄ and H₂SiO₄. For anygiven combination of a source of M4 and a source of M6, a source of Mncan be, but is not limited to, any chloride, bromide, nitrate, orsulfate of manganese, including MnCl₂, MnCl₃, MnCl₄, Mn(NO₃)₃, MnSO₄ andMn₂(SO₄)₃.

In still other embodiments, the templating agent can include asurfactant, such as tetraoctylammonium chloride, ammonium laurylsulfate, or lauryl glucoside. For any templating agent or any source ofM4, M6, or Mn, the solvent can include an organic solvent, such asethanol, diethyl ether, or acetonitrile. Additionally, any embodiment ofthe method for forming a nanowire described above can include anyadditional component in the reaction mixture, such as a base.

Nanowire-forming methods of various embodiments of the inventioncomprise combining a source of M4, a source of M5, a source of M6, atemplating agent, and a solvent in a reaction mixture. In otherembodiments, however, nanowire-forming methods of the present inventioncomprise combining two of a source of M4, a source of M5 and a source ofM6 in the presence of a templating agent and a solvent to form anintermediate nanowire and then combining a remainder of the source ofM4, the source of M5 and the source of M6 with the intermediatenanowire, wherein M4 includes one or more elements selected from Group1, Group 2, Group 3 and Group 4 elements, wherein M5 includes one ormore elements selected from Group 7, and wherein M6 includes one or moreelements selected from Group 5, Group 6, Group 7, Group 8, Group 14 andGroup 15 elements. In an embodiment, an intermediate nanowire is formedby combining the source of M5 and the source of M6 in the presence ofthe templating agent and the solvent, followed by combining theintermediate nanowire with the source of M4.

1. Biological Template

Because peptide sequences have been shown to have specific and selectivebinding affinity for many different types of metal element ions,biological templates incorporating peptide sequences as nucleation sitesare preferred. Moreover, biological templates can be engineered tocomprise pre-determined nucleation sites in pre-determined spatialrelationships (e.g., separated by a few to tens of nanometers).

Both wild type (i.e., naturally occurring) and genetically engineeredbiological templates can be used. As discussed herein, biologicaltemplates such as proteins and bacteriophage can be engineered based ongenetics to ensure control over the type of nucleation sites (e.g., bycontrolling the peptide sequences), their locations on the templates andtheir respective density and/or ratio to other nucleation sites. See,e.g., Mao, C. B. et al., (2004) Science, 303, 213-217; Belcher, A. etal., (2002) Science 296, 892-895; Belcher, A. et al., (2000) Nature 405(6787) 665-668; Reiss et al., (2004) Nanoletters, 4 (6), 1127-1132,Flynn, C. et al., (2003) J. Mater. Sci., 13, 2414-2421; Mao, C. B. etal., (2003) PNAS, 100 (12), 6946-6951, which references are herebyincorporated by reference in their entireties. This allows for theability to control the composition and distribution of the nucleationsites on the biological template.

Thus, biological templates may be particularly advantageous for acontrolled growth of nanowires. Biological templates can be biomolecules(e.g., proteins) as well as multi-molecular structures of a biologicalorigin, including, for example, bacteriophage, virus, amyloid fiber, andcapsid.

(a) Biomolecules

In certain embodiments, the biological templates are biomolecules. Inmore specific embodiments, the biological templates are anisotropicbiomolecules. Typically, a biomolecule comprises a plurality of subunits(building blocks) joined together in a sequence via chemical bonds. Eachsubunit comprises at least two reactive groups such as hydroxyl,carboxylic acid and amino groups, which enable the bond formations thatinterconnect the subunits. Examples of the subunits include, but are notlimited to: amino acids (both natural and synthetic) and nucleotides.Accordingly, in some embodiments, the biomolecule template is a peptide,protein, nucleic acid, polynucleotide, amino acid, antibody, enzyme, orsingle-stranded or double-stranded nucleic acid or any modified and/ordegraded forms thereof.

Because protein synthesis can be genetically directed, proteins can bereadily manipulated and functionalized to contain desired peptidesequences (i.e., nucleation sites) at desired locations within theprimary structure of the protein. The protein can then be assembled toprovide a template.

Thus, in various embodiments, the templates are biomolecules are nativeproteins or proteins that can be engineered to have nucleation sites forspecific ions.

(b) Baceteriophage

In one particular embodiment, the biological template comprises a M13bacteriophage which has or can be engineered to have one or moreparticular peptide sequences to be expressed on the coat proteins. M13bacteriophage is a filamentous bacterial virus that is produced byamplification through E. coli bacteria. It is 880 nm long and 6.7 nm indiameter. The surface of the filamentous phage is mostly composed of itsmajor coat protein, pVIII. 2700 copies of this protein pack around thephage DNA to make a tight and cylindrical shell. The N-termini of pVIIIform a dense periodic display spaced at 2.7 nm. The final five residuesof pVIII are structurally unconstrained and exposed to the solvent,therefore presenting an optimal target for engineering, manipulation,and substrate interaction.

FIG. 6 schematically shows a filamentous bacteriophage 400, in which asingle-stranded DNA core 410 is surrounded by a proteinaceous coat 420.The coat is composed mainly of pVIII proteins 424 that cover the lengthof the bacteriophage. The ends of the bacteriophage are capped by minorcoat proteins 430 (pIII), 440 (pVI), 450 (pVII) and 460 (pIX). Usinggenetic engineering, a library of diverse, novel peptide sequences (upto 10¹² unique peptides) can be expressed on the surface of the phage,so that each individual phage displays at least one unique peptidesequence. These externally facing peptide sequences can be tested,through the iterative steps of screening, amplification andoptimization, for the ability to control nucleation and growth ofspecific catalytic nanowires. Small peptides engineered and presented onthe phage surface provide a dense periodic display of functional groupsthat are available to bind and coordinate with materials for nucleationand synthesis. The large number of groups presented additionallyprovides a potential chelating effect, therefore increasing the affinityof binding. As the nucleation sites are available in solutionco-precipitation of various materials can take place. Furthermore thefilamentous geometry of bacteriophage result in filamentous nanowirestructures of templated materials that present a large surface area forpotential catalytic activity. Controlled display of a large variety ofchemical functional groups, as well as filamentous nature of formedmaterials are potential advantages of the M13 bacteriophage system forcatalytic material synthesis.

For example, in a further embodiment peptide sequences having one ormore particular nucleation sites specific for various ions are expressedon the coat proteins. For example, in one embodiment, the coat proteinis pVIII with peptide sequences having one or more particular nucleationsites specific for various ions bound thereto. In other furtherembodiments, the peptide sequences bound to the coat protein comprise 2or more amino acids, 5 or more amino acids, 10 or more amino acids, 20or more amino acids, or 40 or more amino acids. In other embodiments,the peptide sequences expressed on the coat protein comprise between 2and 40 amino acids, between 5 and 20 amino acids, or between 7 and 12amino acids.

One of the approaches to obtain different types of M13 bacteriophage isto modify the viral genetic code in order to change the amino acidsequence of the major coat protein pVIII. The changes in sequence onlyaffect the N-terminus amino acids of the pVIII protein, which are theones that make the surface of the M13 phage, while the first 45 aminoacids are left unchanged so that the packing of the pVIII proteinsaround the phage is not compromised. By changing the N-terminus aminoacids on the pVIII protein, the surface characteristics of the phage canbe tailored to higher affinities to specific metal ions and thuspromoting selective growth of specific inorganic materials on the phagesurface.

Many short amino acid sequences can be engineered at the pVIIIN-terminus for precipitation of various materials or combinationsthereof. Typical functional groups in amino acids that can be used totailor the phage surface affinity to metal ions include: carboxylic acid(—COOH), amino (—NH₃ ⁺ or —NH₂), hydroxyl (—OH), and/or thiol (—SH)functional groups. Table 13 summarizes a number of exemplary phages usedin the present invention for preparing nanowires of inorganic metaloxides. In certain embodiment, the present disclosure is directed to anyof the peptide sequences in Table 13. Sequences within Table 13 refer tothe amino acid sequence of the pVIII protein (single-letter amino acidcode). Underlined portions indicate the terminal sequence that wasvaried to tailor the phage surface affinity to metal ions. SEQ ID NO 30represents wild type pVIII protein while SEQ ID NO 31 represents wildtype pVIII protein including the signaling peptide portion (bold).

TABLE 13 Phage Surface Protein Sequences SEQ ID NO Sequence 1AEEGSEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIG IKLFKKFTSKAS 2EEGSDDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGI KLFKKFTSKAS 3AEEEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGIK LFKKFTSKAS 4EEEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGIKL FKKFTSKAS 5AEEEEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGI KLFKKFTSKAS 6AEEAEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGI KLFKKFTSKAS 7EEXEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGIK LFKKFTSKAS X = E or G 8AEDDDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGIK LFKKFTSKAS 9AVSGSSPGDDPAKAAFNSLQASATEYIGYAWAMVVVIVGA TIGIKLFKKFTSKAS 10AVSGSSPDSDPAKAAFNSLQASATEYIGYAWAMVVVIVGA TIGIKLFKKFTSKAS 11AGETQQAMEDPAKAAFNSLQASATEYIGYAWAMVVVIVGA TIGIKLFKKFTSKAS 12AAGETQQAMDPAKAAFNSLQASATEYIGYAWAMVVVIVGA TIGIKLFKKFTSKAS 13AEPGHDAVPEDPAKAAFNSLQASATEYIGYAWAMVVVIVG ATIGIKLFKKFTSKAS 14AEDPAEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIG IKLFKKFTSKAS 15AEDPAKDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIG IKLFKKFTSKAS 16AEFEVEADPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 17AEHEAEEDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 18AESEFELDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 19ADNDVDLDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 20ADSDYDGDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 21ADADRDGDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 22ADSDPDGDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 23ADSDTDSDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 24ADKDYDLDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 25AEFEVGADPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 26AGFEGEADPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 27ADGDLDQDPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 28AEFEAEADPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 29AGFEVEADPAKAAFNSLQASATEYIGYAWAMVVVIVGATI GIKLFKKFTSKAS 30AEGDDDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGI KLFKKFTSKAS 31MKKSLVLKASVAVATLVPMLSFA AEGDDDPAKAAFNSLQASATEYIGYAWAMVVVIVGATIGIKLFKKFTSKAS

Amino acid side chains have assorted chemical properties that can beused for material synthesis. Glutamic acid (E) and aspartic acid (D)have carboxylic acid side chains and are therefore negative at neutralpH. Negative residues are attractive to positively charged metal cationsand therefore can nucleate biomineralization. Proline (P) is acyclically constrained amino acid, and as a part of a protein gives itstructural rigidity, potentially contributing to stronger binginginteractions. Furthermore, through such rigidity proline can aid inbringing other functional side chains closer together for bettercoordination. Other amino acids of interest for use in phage-templatedpreparation of nanowires include histidine (H) that has a side chainwith a pKa=6.0 and is very sensitive to the environment and can be madepositive in only a slightly acidic environment. Tryptophan (W) has alarge aromatic and polar side chain that can contribute to synthesis bymetal pi-interactions.

Accordingly, in certain embodiments the present disclosure providesphage sequences useful for templating of catalytic nanowires. In someembodiments, the engineered pVIII sequence comprises at least oneconstraining amino acid (e.g., P) and a repeat of 2 negative amino acids(e.g., E & D). Alanine is the one of the smallest side chain aminoacids, and in some embodiments may be included as a spacer. The negativecharges may be spread on both E & D amino acids as to avoid too manyrepeats of the same amino acid which may contribute to lower yield ofphage. In a variation of the above sequence, Lysine (K) maybe includedin the terminal phage sequence. Lysine has an active amine group, andtherefore can potentially be attractive to higher group transitionmetals (e.g., Pt, Pd, Au) that exist as negatively charged ions insolution.

In other embodiments, the sequences are based on an alternating peptidelibrary approach. The engineered sequence is constrained to have analternating negatively charged residue, for example either AEXEXEX orADXDXDX, wherein X is any amino acid.

In other embodiments, a degenerate library approach is used to detectother viable sequences, i.e. amino acids of interest can be constrainedand others can be left to be chosen by what is biologically favorablefor phage production by bacteria. For example alternate libraries basedon the negative residues AEXEXEX or ADXDXDX can be prepared using adegenerate library approach. In some embodiments, Histidine constrainedor Tryptophan constrained libraries (e.g., AHXHXHX, AWXWXWX, AXXWHWX),are useful for identifying aromatic and hydrophobic interactions. Otherembodiments include altering the placement and order of the amino acids(e.g., ADDXEE), and still other embodiments include constraining thesequences with proline amino acids (e.g., AEPEPEP, ADPDPDP), to explorethe effect of peptide structure on synthesis. Any combination of theabove can be engineered and explored for biological viability and thetemplation behaviors. Non-limiting examples of phage surface proteinsequences useful in the present invention are provided in Table 9 below.

In one embodiment, the present disclosure provides methods forpreparation and purification of filamentous bacteriophage. Thepurification methods may be based on standard methods or on the novelfiltration methods described below. Such filtration methods can beadvantageous in practice of certain embodiments of the invention sincethe methods are amenable to large scale preparations. Standard methodsfor purification of viruses, bacteriophage, DNA and recombinant proteinsfrom feedstock solution generally include several steps. For example,the heavier components of feedstock, such as bacterial cells and celldebris, are first separated by centrifugation. Further, the particles ofinterest are then precipitated from the remaining supernatant by using asolution of polyethylene glycol and salt.

While not wishing to be bound by theory, it is believed thatpolyethylene glycol (PEG) as a big inert molecule adds osmotic stress tothe solution by steric hindrance and increasing crowding, while the highconcentration of salt screens the charge repulsion between theparticles. The concentration of PEG, type and quantity of salts, as wellas the subsequent processing steps depend upon the particularapplication. In the instance of filamentous bacteriophage, its long rodanisotropic geometry allows for minimal quantity of PEG to selectivelyprecipitate these particles from the supernatant remaining aftercentrifugation, that might contain components of nutritious media usedfor amplification, as well as proteins and DNA excreted by bacteriaduring amplification and potential cell lysis. Following theprecipitation, the solution is generally centrifuged once again topellet the particle of interest such as bacteriophage, and thenresuspended in the desired volume of buffer solution.

The standard process described above works well on a small scale,however it may be limited by the centrifuge capacity as it is scaled up.Often the final solution has to be further clarified of remainingbacteria, by further centrifugation or filtration. Additionally thepurified product may contain both trace amounts of polyethylene glycolas well as the salt used for precipitation in quantities difficult toquantitate, yet potentially influencing further chemical processing. Inthe case of bacteriophage, the solution can be purified further by aCsCl gradient and ultracentrifugation, however these steps are sometimesdifficult to scale up due to the volumes that can be processed as wellas the time and cost involved. Accordingly, there remains a need forimproved phage preparation methods which are amenable to large scaleproduction of purified phage.

The novel methods described herein are useful for large scalepreparation of phage. In one embodiment, the method comprises a two-stepfiltration to purify bacteriophage from a feedstock solution. In thefollowing description these two filtration steps are sometimes referredto as the first filtration step and the second filtration step,respectively. In some embodiments, the types of filtration employedcomprise tangential flow filtration (TFF) and/or depth filtration. It isbelieved that such methods have not previously been employed withfilamentous bacteriophage.

Tangential flow filtration is a technique that separates the solutionbased on a size exclusion principle dictated by the pore size of themembrane used. The solution to be filtered is flowed over the membrane,with pressure applied across the membrane. One aspect of TFF is that thesolvent is split in two parts, the retentate and the permeate;therefore, particles in both the retentate and the permeate remain insolution. Particles smaller than the pore size filter through to thepermeate side, and the larger particles are retained in the solution onthe retentate side of the membrane. Fouling of the membrane is minimizedby the continuous flow and recirculation of the solution on theretentate side of the membrane. Depending on the particular application,the particles of interest can be harvested either in the retentate or inthe permeate, since both are still in solution.

Depth filtration also separates the solution based on a size exclusionprinciple dictated by the pore size of the membrane used, but thesolution to be filtered is flowed through the membrane instead oftangentially flowing along it as in TFF. Contrary to TFF, the entireamount of the solution is flowed through the membrane. Particles smallerthan the pore size filter through to the permeate side, and the largerparticles are retained in the solution on the retentate side of themembrane. Accordingly, the main difference between TFF and depthfiltration is the nature of the retentate, which is a solution in TFFand a solid (“cake”) in depth filtration. Typically, in depth filtrationthe particles of interest will be harvested in the permeate and not inthe retentate, which is trapped in the membrane.

In one embodiment, a two-step TFF process for purifying bacteriophage isprovided. In the first step a micro filtration is performed and in thesecond step an ultrafiltration is performed. In this respect amicrofiltration comprises filtering a phage-containing solution throughmembranes of higher pore size (e.g., 0.1 to 3 μm). During this step thebigger particles of the feedstock such as cells and cell debris areclarified from solution and retained in the retentate, while theparticles of interest (e.g., phage) are filtered through with thepermeate. Ultrafiltration refers to filtration using smaller pore sizemembranes (e.g., 1 to 1000 kDa), the size being dependent on thespecific application. During this filtration the particles of interestare retained while smaller particles, such as media components and smallproteins are filtered out. In certain embodiments the ultrafiltrationstep can also be used to concentrate the solution by filtering outwater. In an optional third step, diafiltration may be used to exchangethe remaining concentrated media for buffer solution. Diafiltration maybe performed over the same membrane as ultrafiltration.

Various parameters of the foregoing filtration process may be varied foroptimal purification results. In some embodiments, for bothmicrofiltration and ultrafiltration, parameters that control the flow ofmaterial over and through the membrane are important and can be varied.For example, the transmembrane pressure that is seen by the membrane aswell as the flow rate of the recirculating solution can be varied from 0to 40 psig and 100 to 3500 μL/h/m².

One embodiment of the present disclosure provides a tangential flowfiltration process that is easily scalable. In this embodiment, thevolume of the feedstock that can be processed in a given time, scalesdirectly with the surface area of the membrane used. As the surface areais increased and the flow rate adjusted accordingly, the otherparameters of the process may remain the same. This allows for amanufacturing process to be initially designed and optimized using labscale equipment and then later directly scaled to larger scales.

In one embodiment of the foregoing filtration purification process forM13 phage, both the microfiltration and the ultrafiltration areperformed using TFF. For microfiltration, a nylon flat sheet membranecartridge having pore sizes ranging from 0.1 to 3 μm, 0.1 to 1 μm or 0.2to 0.45 μm may be used. In some embodiments, the flow rate inmicrofiltration ranges from 100 to 3500 L/h/m², 300 to 3000 l/h/m² or500 to 2500 l/h/m². In some embodiments, the flow rate inmicrofiltration is about 550 L/h/m². In other embodiments, thetransmembrane pressure in microfiltration ranges from 1 to 30 psig orfrom 2 to 20 psig, and in some embodiments the transmembrane pressure isabout 15 psig.

For the ultrafiltration and diafiltration steps a polyethersulfone flatsheet membrane cartridge having pore sizes ranging from 100 to 1000 kDamay be used. In some embodiments, the cartridge comprises pores havingsizes of about 500 kDa. Flow parameters of approximately 100 to 3500L/h/m², 300 to 3000 l/h/m² or 500 to 2500 l/h/m², for example about 2200Llhr/m² may be used. The transmembrane pressures range from 1 to 30 psigor from 2 to 20 psig, and in some embodiments the transmembrane pressureis about 6 psig. In some embodiments, the solution may be diafilteredwith from 1 to 20 volumes of water, for example 10 volumes of water. Theoptimum number of volumes depends on the desired purity of the finalproduct. Any of the above parameters including the membrane material andconfiguration as well as flow parameters can be altered depending on theapplication, the particle of interest and purity and yield desired inthe final product.

In another embodiment, the microfiltration step is performed with depthfiltration instead of TFF to eliminate bacterial cells and cell debris.The depth filtration may be performed using two filters connected inseries. In some embodiments, the first filter comprises a glass fibercapsule with nominal porosity of from 0.5 to 3 μm, for example about 1.2μm and followed by a double membrane filter capsule having, eachmembrane filter capsule having a pore size of from 0.1 to 1 μm, forexample about 0.8 μm and about 0.45 μm, respectively. This filtrationsystem allows for clarification of the feedstock solution prior to theultrafiltration step, which may be carried out using the same parametersdescribed in any of the embodiments described herein.

Any of the above parameters may be modified to arrive at otherembodiments. For example, in the initial step of clarifying the solutionof cells and cell debris either TFF or depth filtration can be used. Forthe 2nd step of purifying the filamentous bacteriophage from theremaining solution TFF or depth filtration may also be used; however, incertain embodiments TFF is used.

The disclosed filtration purification methods can be applied to anyother biological particles that are currently purified using acombination of centrifugation and precipitation methods. Such biologicalparticles include, but are not limited to, other bacteriophage (i.e.,not just M13), viruses, proteins, etc. The filter membrane geometry canbe either a flat sheet or hollow fiber.

In some embodiments, the membranes used for TFF are chemicallyactivated, via charge or affinity molecules, and such membranes mayexhibit preferential binding to particles of interest to either befiltered out or retained. In other embodiments, the filter materialsused for depth filtration may be activated, via charge or affinitymolecules and may exhibit preferential binding for particles to befiltered out. Furthermore, some embodiments employ membranes for TFFwhich are mechanically activated via vibration to reduce fouling andenhance filtration.

(c) Amyloid Fibers

In another embodiment, amyloid fibers can be used as the biologicaltemplate on which metal ions can nucleate and assemble into a catalyticnanowire. Under certain conditions, one or more normally solubleproteins (i.e., a precursor protein) may fold and assemble into afilamentous structure and become insoluble. Amyloid fibers are typicallycomposed of aggregated β-strands, regardless of the structure origin ofthe precursor protein. As used herein, the precursor protein may containnatural or unnatural amino acids. The precursor protein may be furthermodified with a fatty acid tail.

(d) Virus and Capsid

In further embodiments, a virus or a capsid can be used as a biologicaltemplate. Similar to a bacteriophage, a virus also comprises a proteincoat and a nucleic acid core. In particular, viruses of anisotropicshapes, such as viral fibers, are suitable for nucleating and growingthe catalytic nanowires described herein. Further, a virus can begenetically manipulated to express specific peptides on its coat fordesirable binding to the ions. Viruses that have elongated orfilamentous structures include those that are described in, for example,Christopher Ring, Genetically Engineered Viruses, (Ed) Bios Scientific(2001).

In certain embodiments, the virus may have its genetic materials removedand only the exterior protein coat (capsid) remains as the biologicaltemplate.

2. Nucleation

Nucleation is the process of forming an inorganic nanowire in situ byconverting soluble precursors (e.g., metal salts and anions) intonanocrystals in the presence of a template (e.g., a biologicaltemplate). Typically, the nucleation and growth takes place frommultiple binding sites along the length of the biological template inparallel. The growth continues until a structure encasing the biologicaltemplate is formed. In some embodiments this structure issingle-crystalline. In other embodiments the structure is amorphous, andin other embodiments the structure is polycrystalline. If desired, uponcompletion of the synthesis the organic biological template (e.g.,bacteriophage) can be removed by thermal treatment (˜300° C.) in air oroxygen, without significantly affecting either the structure or shape ofthe inorganic material. In addition, dopants can be eithersimultaneously incorporated during the growth process or, in anotherembodiment, dopants can be incorporated via impregnation techniques.

(a) Nanowire Growth Methods

FIG. 7 shows a flow chart of a nucleation process for forming a nanowirecomprising a metal oxide. A phage solution is first prepared (block504), to which metal salt precursor comprising metal ions is added(block 510). Thereafter, an anion precursor is added (block 520). It isnoted that, in various embodiments, the additions of the metal ions andanion precursor can be simultaneous or sequentially in any order. Underappropriate conditions (e.g., pH, molar ratio of the phage and metalsalt, molar ratio of the metal ions and anions, addition rate, etc.),the metal ions and anions become bound to the phage, nucleate and growinto a nanowire of M_(m)X_(n)Z_(p) composition (block 524). Followingcalcinations, nanowires comprising M_(m)X_(n) are transformed tonanowires comprising metal oxide (M_(x)O_(y)) (block 530). An optionalstep of doping (block 534) incorporates a dopant (D^(p+)) in thenanowires comprising metal oxide (M_(x)O_(y), wherein x and y are eachindependently a number from 1 to 100. For ease of illustration, FIG. 7depicts calcinations prior to doping; however, in certain embodimentsdoping may be performed prior to calcinations.

In one embodiment, a method for preparing inorganic catalyticpolycrystalline nanowires is provided, the nanowires each having a ratioof effective length to actual length of less than one and an aspectratio of greater than ten as measured by TEM in bright field mode at 5keV, wherein the nanowires each comprise one or more elements selectedfrom Groups 1 through 7, lanthanides, actinides or combinations thereof.The method comprises:

admixing (A) with a mixture comprising (B) and (C);

admixing (B) with a mixture comprising (A) and (C); or

admixing (C) with a mixture comprising (A) and (B) to obtain a mixturecomprising (A), (B) and (C), wherein (A), (B), and (C) comprise,respectively:

(A) a biological template;

(B) one or more salts comprising one or more metal elements from any ofGroups 1 through 7, lanthanides, actinides or combinations thereof; and

(C) one or more anion precursors.

Another embodiment provides a method for preparing a nanowire comprisinga metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metalcarbonate, the method comprising:

a) providing a solution comprising a plurality of biological templates;

(b) introducing at least one metal ion and at least one anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a nanowire comprising a plurality of metalsalts (M_(m)X_(n)Z_(p)) on the template; and

(c) converting the nanowire (M_(m)X_(n)Z_(p)) to a nanowire comprising aplurality of metal oxides (M_(x)O_(y)), metal oxy-hydroxides(M_(x)O_(y)OH_(z)), metal oxycarbonates (M_(x)O_(y)(CO₃)_(z)), metalcarbonate (M_(x)(CO₃)_(y)) or combinations thereof

wherein:

M is, at each occurrence, independently a metal element from any ofGroups 1 through 7, lanthanides or actinides;

X is, at each occurrence, independently hydroxide, carbonate,bicarbonate, phosphate, hydrogenphosphate, dihydrogenphosphate, sulfate,nitrate or oxalate;

Z is O;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In certain variations of the foregoing, two or more different metal ionsmay be used. This produces nanowires comprising a mixture of two or moremetal oxides. Such nanowires may be advantageous in certain catalyticreactions. For example, in some embodiments the nanowire catalysts maycomprise at least a first and second metal oxide wherein the first metaloxide has better OCM activity than the second metal oxide and the secondmetal oxide has better ODH activity than the first metal oxide. Incertain embodiments of the above, Applicants have found that it may beadvantageous to perform multiple sequential additions of the metal ion,This addition technique may be particularily applicable to embodimentswherein two or more different metal ions are employed to form a mixednanowire (M1M2X_(x)Y_(y), wherein M1 and M2 are different metalelements), which can be converted to M1M2O_(z), for example bycalcination. The slow addition may be performed over any period of time,for example from 1 day to 1 week. In this regard, use of a syringe pumpor an automatic (e.g., robotic) liquid dispenser may be advantageous.Slow addition of the components help ensure that they will nucleate onthe biological template instead of non-selectively precipitate.

In various embodiments, the biological templates are phages, as definedherein. In further embodiments, the metal ion is provided by adding oneor more metal salt (as described herein) to the solution. In otherembodiments, the anion is provided by adding one or more anion precursorto the solution. In various embodiments, the metal ion and the anion canbe introduced to the solution simultaneously or sequentially in anyorder. In some embodiments, the nanowire (M_(m)X_(n)Z_(p)) is convertedto a metal oxide nanowire by calcination, which is a thermal treatmentthat transforms or decomposes the M_(m)X_(n)Z_(p) nanowire to a metaloxide. In yet another embodiment, the method further comprises dopingthe metal oxide nanowire with a dopant. Doping may be performed eitherbefore or after calcination. Converting the nanowire to a metal oxide(or oxy-hydroxide, oxy-carbonate, or carbonate, etc.) generallycomprises calcining.

In a variation of the above method, mixed metal oxides can be prepared(as opposed to a mixture of metal oxides). Mixed metal oxides can berepresented by the following formula M1_(w)M2_(x)M3_(y)O_(z), whereinM1, M2 and M3 are each independently absent or a metal element, and w,x, y and z are integers such that the overall charge is balanced. Mixedmetal oxides comprising more than three metals are also contemplated andcan be prepared via an analogous method. Such mixed metal oxides findutility in a variety of the catalytic reactions disclosed herein. Oneexemplary mixed metal oxide is Na₁₀MnW₅O₁₇ (Example 18).

Thus, one embodiment provides a method for preparing a mixed metal oxidenanowire comprising a plurality of mixed metal oxides(M1_(w)M2_(x)M3_(y)O_(z)), the method comprising:

a) providing a solution comprising a plurality of biological templates;

(b) introducing metal salts comprising M1, M2 and M3 to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a nanowire comprising a plurality of the metal salts on thetemplate; and

(c) converting the nanowire to a mixed metal oxide nanowire comprising aplurality of mixed metal oxides (M1_(w)M2_(x)M3_(y)O_(z)),

wherein:

M1, M2 and M3 are, at each occurrence, independently a metal elementfrom any of Groups 1 through 7, lanthanides or actinides;

n, m, x and y are each independently a number from 1 to 100; and

p is a number from 0 to 100.

In other embodiments, the present disclosure provides a method forpreparing metal oxide nanowires which may not require a calcinationstep. Thus, in some embodiments the method for preparing metal oxidenanowires comprises:

(a) providing a solution that includes a plurality of biologicaltemplates; and

(b) introducing a compound comprising a metal to the solution underconditions and for a time sufficient to allow for nucleation and growthof a nanowire (M_(m)Y_(n)) on the template;

wherein:

M is a metal element from any of Groups 1 through 7, lanthanides oractinides;

Y is O;

n and m are each independently a number from 1 to 100.

In some specific embodiments of the foregoing method, M is an earlytransition metal, for example V, Nb, Ta, Ti, Zr, Hf, W, Mo or Cr. Inother embodiments, the metal oxide is WO₃. In yet another embodiment,the method further comprises doping the metal oxide nanowire with adopant. In some further embodiments, a reagent is added which convertsthe compound comprising a metal into a metal oxide.

In another embodiment, nanowires are prepared by using metal saltssensitive to water hydrolysis, for example NbCl₅, WCl₆, TiCl₄, ZrCl₄. Atemplate can be placed in ethanol along with the metal salt. Water isthen slowly added to the reaction in order to convert the metals saltsto metal oxide coated template.

By varying the nucleation conditions, including (without limitation):incubation time of phage and metal salt; incubation time of phage andanion; concentration of phage; metal ion concentration, anionconcentration, sequence of adding anion and metal ions; pH; phagesequences; solution temperature in the incubation step and/or growthstep; types of metal precursor salt; types of anion precursor; additionrate; number of additions; amount of metal salt and/or anion precursorper addition, the time that lapses between the additions of the metalsalt and anion precursor, including, e.g., simultaneous (zero lapse) orsequential additions followed by respective incubation times for themetal salt and the anion precursor, stable nanowires of diversecompositions and surface properties can be prepared. For example, incertain embodiments the pH of the nucleation conditions is at least 7.0,at least 8.0, at least 9.0, at least 10.0, at least 11.0, at least 12.0or at least 13.0.

As noted above, the rate of addition of reactants (e.g., metal salt,metal oxide, anion precursor, etc.) is one parameter that can becontrolled and varied to produce nanowires having different properties.During the addition of reactants to a solution containing an existingnanowire and/or a templating material (e.g., phage), a criticalconcentration is reached for which the speed of deposition of solids onthe existing nanowire and/or templating material matches the rate ofaddition of reactants to the reaction mixture. At this point, theconcentration of soluble cation stabilizes and stops rising. Thus,nanowire growth can be controlled and maximized by maintaining the speedof addition of reactants such that near super-saturation concentrationof the cation is maintained. This helps ensure that no undesirablenucleation occurs. If super-saturation of the anion (e.g., hydroxide) isexceeded, a new solid phase can start nucleating which allows fornon-selective solid precipitation, rather than nanowire growth. Thus, inorder to selectively deposit an inorganic layer on an existing nanowireand/or a templating material, the addition rate of reactants should becontrolled to avoid reaching super-saturation of the solution containingthe suspended solids.

Accordingly, in one embodiment, reactant is repeatedly added in smalldoses to slowly build up the concentration of the reactant in thesolution containing the template. In some embodiments, the speed ofaddition of reactant is such that the reactant concentration in thesolution containing the template is near (but less than) the saturationpoint of the reactant. In some other embodiments, the reactant is addedportion wise (i.e., step addition) rather than continuously. In theseembodiments, the amount of reactant in each portion, and the timebetween addition of each portion, is controlled such that the reactantconcentration in the solution containing the template is near (but lessthan) the saturation point of the reactant. In certain embodiments ofthe foregoing, the reactant is a metal cation while in other embodimentsthe reactant is an anion.

Initial formation of nuclei on a template can be obtained by the samemethod described above, wherein the concentration of reactant isincreased until near, but not above, the supersaturation point of thereactant. Such an addition method facilitates nucleation of the solidphase on the template, rather than homogeneous non-seeding nucleation.In some embodiments, it is desirable to use a slower reactant additionspeed during the initial nucleation phase as the super-saturationdepression due to the template might be quite small at this point. Oncethe first layer of solid (i.e., nanowire) is formed on the template, theaddition speed can be increased.

In some embodiments, the addition rate of reactant is controlled suchthat the precipitation rate matches the addition rate of the reactant.In these embodiments, nanowires comprising two or more different metalscan be prepared by controlling the addition rates of two or moredifferent metal cation solutions such that the concentration of eachcation in the templating solution is maintained at or near (but does notexceed) the saturation point for each cation.

In some embodiments, the optimal speed of addition (and step size ifusing step additions) is controlled as a function of temperature. Forexample, in some embodiments the nanowire growth rate is accelerated athigher temperatures. Thus, the addition rate of reactants is adjustedaccording to the temperature of the templating solution.

In other embodiments, modeling (iterative numeric rather than algebraic)of the nanowire growth process is used to determine optimal solutionconcentrations and supernatant re-cycling strategies.

As noted above, the addition rate of reactants can be controlled andmodified to change the properties of the nanowires. In some embodiments,the addition rate of a hydroxide source must be controlled such that thepH of the templating solution is maintained at the desired level. Thismethod may require specialized equipment, and depending on the additionrate, the potential for localized spikes in pH upon addition of thehydroxide source is possible. Thus, in an alternative embodiment thepresent disclosure provides a method wherein the template solutioncomprises a weak base that slowly generates hydroxide in-situ, obviatingthe need for an automated addition sequence.

In the above embodiment, organic epoxides, such as but not limited topropylene oxide and epichlorohydrin, are used to slowly increase thetemplate solution pH without the need for automated pH control. Theepoxides are proton scavengers and undergo an irreversible ring-openingreaction with a nucleophilic anion of the metal oxide precursor (such asbut not limited to Cl⁻ or NO₃ ⁻). The net effect is a slow homogenousraise in pH to form metal hydroxy species in solution that deposit ontothe template surface. In some embodiments, the organic epoxide ispropylene oxide.

An attractive feature of this method is that the organic epoxide can beadded all at once, there is no requirement for subsequent additions oforganic epoxide to grow metal oxide coatings over the course of thereaction. Due to the flexibility of the “epoxide-assisted” coatings, itis anticipated that many various embodiments can be employed to make newtemplated materials (e.g., nanowires). For example, mixed metal oxidenanowires can be prepared by starting with appropriate ratios of metaloxide precursors and propylene oxide in the presence of bacteriophage.In other embodiments, metal oxide deposition on bacteriophage can bedone sequentially to prepare core/shell materials (described in moredetail below).

(b) Metal Salt

As noted above, the nanowires are prepared by nucleation of metal ionsin the presence of an appropriate template, for example, abacteriophage. In this respect, any soluble metal salt may be used asthe precursor of metal ions that nucleate on the template. Soluble metalsalts of the metals from Groups 1 through 7, lanthanides and actinidesare particularly useful and all such salts are contemplated.

In one embodiment, the soluble metal salt comprises chlorides, bromides,iodides, nitrates, sulfates, acetates, oxides, oxyhalides, oxynitrates,phosphates (including hydrogenphosphate and dihydrogenphosphate)formates, alkoxides or oxalates of metal elements from Groups 1 through7, lanthanides, actinides or combinations thereof. In more specificembodiments, the soluble metal salt comprises chlorides, nitrates orsulfates of metal elements from Groups 1 through 7, lanthanides,actinides or combinations thereof. The present disclosure contemplatesall possible chloride, bromide, iodide, nitrate, sulfate, acetate,oxide, oxyhalides, oxynitrates, phosphates (including hydrogenphosphateand dihydrogenphosphate) formates, alkoxides and oxalate salts of metalelements from Groups 1 through 7, lanthanides, actinides or combinationsthereof.

In another embodiment, the metal salt comprises LiCl, LiBr, LiI, LiNO₃,Li₂SO₄, LiCO₂CH₃, Li₂C₂O₄, Li₃PO₄, Li₂HPO₄, LiH₂PO₄, LiCO₂H, LiOR, NaCl,NaBr, NaI, NaNO₃, Na₂SO₄, NaCO₂CH₃, Na₂C₂O₄, Na₃PO₄, Na₂HPO₄, NaH₂PO₄,NaCO₂H, NaOR, KCl, KBr, KI, KNO₃, K₂SO₄, KCO₂CH₃, K₂C₂O₄, K₃PO4, K₂HPO₄,KH₂PO₄, KCO₂H, KOR, RbCl, RbBr, RbI, RbNO₃, Rb₂SO₄, RbCO₂CH₃, Rb₂C₂O₄,Rb₃PO₄, Rb₂HPO₄, RbH₂PO₄, RbCO₂H, RbOR, CsCl, CsBr, CsI, CsNO₃, Cs₂SO₄,CsCO₂CH₃, Cs₂C₂O₄, Cs₃PO₄, Cs₂HPO₄, CsH₂PO₄, CsCO₂H, CsOR, BeCl₂, BeBr₂,BeI₂, Be(NO₃)₂, BeSO₄, Be(CO₂CH₃)₂, BeC₂O₄, Be₃(PO4)₂, BeHPO₄,Be(H₂PO₄)₂, Be(CO₂H)₂, Be(OR)₂, MgCl₂, MgBr₂, MgI₂, Mg(NO₃)₂, MgSO₄,Mg(CO₂CH₃)₂, MgC₂O₄, Mg₃(PO₄)₂, MgHPO₄, Mg(H₂PO₄)₂, Mg(CO₂H)₂, Mg(OR)₂,CaCl₂, CaBr₂, CaI₂, Ca(NO₃)₂, CaSO₄, Ca(CO₂CH₃)₂, CaC₂O₄, Mg₃(PO₄)₂,MgHPO₄, Mg(H₂PO₄)₂, Mg(CO₂H)₂, Mg(OR)₂, SrCl₂, SrBr₂, SrI₂, Sr(NO₃)₂,SrSO₄, Sr(CO₂CH₃)₂, SrC₂O₄, Sr₃(PO₄)₂, SrHPO₄, Sr(H₂PO₄)₂, Sr(CO₂H)₂,Sr(OR)₂, BaCl₂, BaBr₂, BaI₂, Ba(NO₃)₂, BaSO₄, Ba(CO₂CH₃)₂, BaC₂O₄,Ba₃(PO₄)₂, BaHPO₄, Ba(H₂PO₄)₂, Ba(CO₂H)₂, Ba(OR)₂, ScCl₃, ScBr₃, ScI₃,Sc(NO₃)₃, Sc₂(SO₄)₃, Sc(CO₂CH₃)₃, Sc₂(C₂O₄)₃, ScPO₄, Sc₂(HPO₄)₃,Sc(H₂PO₄)₃, SC(CO₂H)₃, SC(OR)₃, YCl₃, YBr₃, YI₃, Y(NO₃)₃, Y₂(SO₄)₃,Y(CO₂CH₃)₃, Y₂(C₂O₄)₃, YPO₄, Y₂(HPO₄)₃, Y(H₂PO₄)₃, Y(CO₂H)₃, Y(OR)₃,TiCl₄, TiBr₄, TiI₄, Ti(NO₃)₄, Ti(SO₄)₂, Ti(CO₂CH₃)₄, Ti(C₂O₄)₂,Ti₃(PO₄)₄, Ti(HPO₄)₂, Ti(H₂PO₄)₄, Ti(CO₂H)₄, Ti(OR)₄, ZrCl₄, ZrOCl₂,ZrBr₄, ZrI₄, Zr(NO₃)₄, ZrO(NO₃)₂, Zr(SO₄)₂, Zr(CO₂CH₃)₄, Zr(C₂O₄)₂,Zr₃(PO₄)₄, Zr(HPO₄)₂, Zr(H₂PO₄)₄, Zr(CO₂H)₄, Zr(OR)₄, HfCl₄, HfBr₄,HfI₄, Hf(NO₃)₄, Hf(SO₄)₂, Hf(CO₂CH₃)₄, Hf(C₂O₄)₂, Hf₃(PO₄)₄, Hf(HPO₄)₂,Hf(H₂PO₄)₄, Hf(CO₂H)₄, Hf(OR)₄, LaCl₃, LaBr₃, LaI₃, La(NO₃)₃, La₂(SO₄)₃,La(CO₂CH₃)₃, La₂(C₂O₄)₃, LaPO₄, La₂(HPO₄)₃, La(H₂PO₄)₃, La(CO₂H)₃,La(OR)₃, WCl₂, WCl₃, WCl₄, WCl₅, WCl₆, WBr₂, WBr₃, WBr₄, WBr₅, WBr₆,WI₂, WI₃, WI₄, WI₅, WI₆, W(NO₃)₂, W(NO₃)₃, W(NO₃)₄, W(NO₃)₅, W(NO₃)₆,W(CO₂CH₃)₂, W(CO₂CH₃)₃, W(CO₂CH₃)₄, W(CO₂CH₃)₅, W(CO₂CH₃)₆, WC₂O₄,W₂(C₂O₄)₃, W(C₂O₄)₂, W₂(C₂O₄)₅, W(C₂O₄)₆, WPO₄, W₂(HPO₄)₃, W(H₂PO₄)₃,W(CO₂H)₃, W(OR)₃, W₃(PO₄)₄, W(HPO₄)₂, W(H₂PO₄)₄, W(CO₂H)₄, W(OR)₄,W₃(PO₄)₅, W₂(HPO₄)₅, W(H₂PO₄)₅, W(CO₂H)₅, W(OR)₅, W(PO₄)₂, W(H₃PO₄)₃,W(H₂PO₄)₆, W(CO₂H)₆, W(OR)₆, MnCl₂ MnCl₃, MnBr₂ MnBr₃, MnI₂ MnI₃,Mn(NO₃)₂, Mn(NO₃)₃, MnSO₄, Mn₂(SO₄)₃, Mn(CO₂CH₃)₂, Mn(CO₂CH₃)₃, MnC₂O₄,Mn₂(C₂O₄)₃, Mn₃(PO₄)₂, MnHPO₄, Mn(H₂PO₄)₂, Mn(CO₂H)₂, Mn(OR)₂, MnPO₄,Mn₂(HPO₄)₃, Mn(H₂PO₄)₃, Mn(CO₂H)₃, Mn(OR)₃, MoCl₂, MoCl₃, MoCl₄, MoCl₅,MoBr₂, MoBr₃, MoBr₄, MoBr₅, MoI₂, MoI₃, MoI₄, MoI₅, Mo(NO₃)₂, Mo(NO₃)₃,Mo(NO₃)₄, Mo(NO₃)₅, MoSO₄, Mo₂(SO₄)₃, Mo(SO₄)₂, Mo₂(SO₄)₅, Mo(CO₂CH₃)₂,Mo(CO₂CH₃)₃, Mo(CO₂CH₃)₄, Mo(CO₂CH₃)₅, MoC₂O₄, Mo₂(C₂O₄)₃, Mo(C₂O₄)₂,MO₂(C₂O₄)₅, Mo₃(PO₄)₂, MoHPO₄, Mo(H₂PO₄)₂, Mo(CO₂H)₂, Mo(OR)₂, MoPO₄,Mo₂(HPO₄)₃, Mo(H₂PO₄)₃, Mo(CO₂H)₃, Mo(OR)₃, Mo₃(PO₄)₄, Mo(HPO₄)₂,Mo(H₂PO₄)₄, Mo(CO₂H)₄, Mo(OR)₄, Mo₃(PO₄)₅, Mo₂(HPO₄)₅, Mo(H₂PO₄)₅,Mo(CO₂H)₅, Mo(OR)₅, VCl, VCl₂, VCl₃, VCl₄, VCl₅ VBr, VBr₂, VBr₃, VBr₄,VBr₅, VI₃ VI₂, VI₃, VI₄, VI₅, VNO₃, V(NO₃)₂, V(NO₃)₃, V(NO₃)₄, V(NO₃)₅,V₂SO₄, VSO₄, V₂(SO₄)₃, V(SO₄)₄, VCO₂CH₃, V(CO₂CH₃)₂, V(CO₂CH₃)₃,V(CO₂CH₃)₄, V₂C₂O₄, VC₂O₄, V₂(C₂O₄)₃, V(C₂O₄)₄, V₃PO₄, V₂HPO₄₃ VH₂PO₄,VCO₂H, VOR, V₃(PO₄)₂, VHPO₄, V(H₂PO₄)₂, V(CO₂H)₂, V(OR)₂, VPO₄,V₂(HPO₄)₃, V(H₂PO₄)₃, V(CO₂H)₃, V(OR)₃, V₃(PO₄)₄, V(HPO₄)₂, V(H₂PO₄)₄,V(CO₂H)₄, V(OR)₄, V₃(PO₄)₅, V₂(HPO₄)₅, V(H₂PO₄)₅, V(CO₂H)₅, V(OR)₅,TaCl, TaCl₂, TaCl₃, TaCl₄, TaCl₅, TaBr, TaBr₂, TaBr₃, TaBr₄, TaBr₅, TaI,TaI₂, TaI₃, TaI₄, TaI₅, TaNO₃, Ta(NO₃)₂, Ta(NO₃)₃, Ta(NO₃)₄, Ta(NO₃)₅,Ta₂SO₄, TaSO₄, Ta₂(SO₄)₃, Ta(SO₄)₄, TaCO₂CH₃, Ta(CO₂CH₃)₂, Ta(CO₂CH₃)₃,Ta(CO₂CH₃)₄, Ta₂C₂O₄, TaC₂O₄, Ta₂(C₂O₄)₃, Ta(C₂O₄)₄, Ta₃PO₄, Ta₂HPO₄,TaH₂PO₄, TaCO₂H, TaOR, Ta₃(PO₄)₂, TaHPO₄, Ta(H₂PO₄)₂, Ta(CO₂H)₂,Ta(OR)₂, TaPO₄, Ta₂(HPO₄)₃, Ta(H₂PO₄)₃, Ta(CO₂H)₃, Ta(OR)₃, Ta₃(PO₄)₄,Ta(HPO₄)₂, Ta(H₂PO₄)₄, Ta(CO₂H)₄, Ta(OR)₄, Ta₃(PO₄)₅, Ta₂(HPO₄)₅,Ta(H₂PO₄)₅, Ta(CO₂H)₅, Ta(OR)₅, NbCl, NbCl₂, NbCl₃, NbCl₄, NbCl₅, NbBr,NbBr₂, NbBr₃, NbBr₄, NbBr₅, NbI, NbI₂, NbI₃, NbI₄, NbI₅, NbNO₃,Nb(NO₃)₂, Nb(NO₃)₃, Nb(NO₃)₄, Nb(NO₃)₅, Nb₂SO₄, NbSO₄, Nb₂(SO₄)₃,Nb(SO₄)₄, NbCO₂CH₃, Nb(CO₂CH₃)₂, Nb(CO₂CH₃)₃, Nb(CO₂CH₃)₄, Nb₂C₂O₄,NbC₂O₄, Nb₂(C₂O₄)₃, Nb(C₂O₄)₄, Nb₃PO₄, Nb₂HPO₄, NbH₂PO₄, NbCO₂H, NbOR,Nb₃(PO₄)₂, NbHPO₄, Nb(H₂PO₄)₂, Nb(CO₂H)₂, Nb(OR)₂, NbPO₄, Nb₂(HPO₄)₃,Nb(H₂PO₄)₃, Nb(CO₂H)₃, Nb(OR)₃, Nb₃(PO₄)₄, Nb(HPO₄)₂, Nb(H₂PO₄)₄,Nb(CO₂H)₄, Nb(OR)₄, Nb₃(PO₄)₅, Nb₂(HPO₄)₅, Nb(H₂PO₄)₅, Nb(CO₂H)₅,Nb(OR)₅, NdCl₃, NdBr₃, NdI₃, Nd(NO₃)₃, Nd₂(SO₄)₃, Nd(CO₂CH₃)₃,Nd₂(C₂O₄)₃, NdPO₄, Nd₂(HPO₄)₃, Nd(H₂PO₄)₃, Nd(CO₂H)₃, Nd(OR)₃, EuCl₃,EuBr₃, EuI₃, Eu(NO₃)₃, Eu₂(SO₄)₃, Eu(CO₂CH₃)₃, Eu₂(C₂O₄)₃, NdPO₄,Nd₂(HPO₄)₃, Nd(H₂PO₄)₃, Nd(CO₂H)₃, Nd(OR)₃, PrCl₃, PrBr₃, PrI₃,Pr(NO₃)₃, Pr₂(SO₄)₃, Pr(CO₂CH₃)₃, Pr₂(C₂O₄)₃, PrPO₄, Pr₂(HPO₄)₃,Pr(H₂PO₄)₃, Pr(CO₂H)₃, Pr(OR)₃, SmCl₃, SmBr₃, SmI₃, Sm(NO₃)₃, Sm₂(SO₄)₃,Sm(CO₂CH₃)₃, Sm₂(C₂O₄)₃, SmPO₄, Sm₂(HPO₄)₃, Sm(H₂PO₄)₃, Sm(CO₂H)₃,Sm(OR)₃, CeCl₃, CeBr₃, CeI₃, Ce(NO₃)₃, Ce₂(SO₄)₃, Ce(CO₂CH₃)₃,Ce₂(C₂O₄)₃ CePO₄, Ce₂(HPO₄)₃, Ce(H₂PO₄)₃, Ce(CO₂H)₃, Ce(OR)₃, orcombinations thereof, wherein R is alkyl, alkenyl, alkynyl or aryl.

In more specific embodiments, the metal salt comprises MgCl₂, LaCl₃,ZrCl₄, WCl₄, MoCl₄, MnCl₂ MnCl₃, Mg(NO₃)₂, La(NO₃)₃, ZrOCl₂, Mn(NO₃)₂,Mn(NO₃)₃, ZrO(NO₃)₂, Zr(NO₃)₄, or combinations thereof.

In other embodiments, the metal salt comprises NdCl₃, NdBr₃, NdI₃,Nd(NO₃)₃, Nd₂(SO₄)₃, Nd(CO₂CH₃)₃, Nd₂(C₂O₄)₃, EuCl₃, EuBr₃, EuI₃,Eu(NO₃)₃, Eu₂(SO₄)₃, Eu(CO₂CH₃)₃, Eu₂(C₂O₄)₃, PrCl₃, PrBr₃, PrI₃,Pr(NO₃)₃, Pr₂(SO₄)₃, Pr(CO₂CH₃)₃, Pr₂(C₂O₄)₃ or combinations thereof.

In still other embodiments, the metal salt comprises Mg, Ca, Mg, W, La,Nd, Sm, Eu, W, Mn, Zr or mixtures thereof. The salt may be in the formof (oxy)chlorides, (oxy)nitrates or tungstates.

(c) Anion Precursor

The anions, or counter ions of the metal ions that nucleate on thetemplate, are provided in the form of an anion precursor. The anionprecursor dissociates in the solution phase and releases an anion. Thus,the anion precursor can be any stable soluble salts having the desiredanion. For instance, bases such as alkali metal hydroxides (e.g., sodiumhydroxide, lithium hydroxide, potassium hydroxides) and ammoniumhydroxide are anion precursors that provide hydroxide ions fornucleation. Alkali metal carbonates (e.g., sodium carbonate, potassiumcarbonates) and ammonium carbonate are anion precursors that providecarbonates ions for nucleation.

In certain embodiments, the anion precursor comprises one or more metalhydroxide, metal carbonate, metal bicarbonate, metal sulfate, metalphosphate or metal oxalate. Preferably, the metal is an alkali or analkaline earth metal. Thus, the anion precursor may comprise any one ofalkali metal hydroxides, carbonates, bicarbonates, sulfates, phosphatesor oxalate; or any one of alkaline earth metal hydroxides, carbonates,bicarbonates, sulfates, phosphates or oxalates.

In some specific embodiments, the one or more anion precursors compriseLiOH, NaOH, KOH, Sr(OH)₂, Ba(OH)₂, Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃(NR₄)₂CO₃, and NR₄OH, wherein each R is independently selected from H,C₁-C₁₈ alkyl, C₁-C₁₈ alkenyl, C₁-C₁₈ alkynyl and C₁-C₁₈ aryl. Ammoniumsalts may provide certain advantages in that there is less possibilityof introducing unwanted metal impurities. Accordingly, in a furtherembodiment, the anion precursor comprises ammonium hydroxide or ammoniumcarbonate.

The dimensions of the nanowires are comparable to those of thebiological templates (e.g., phage), although they can have differentaspect ratios as longer growth can be used to increase the diameterwhile the length will increase in size at a much slower rate. Thespacing of peptides on the phage surface controls the nucleationlocation and the catalytic nanowire size based on steric hindrance. Thespecific peptide sequence information can (or may) dictate the identity,size, shape and crystalline face of the catalytic nanowire beingnucleated. To achieve the desired stochiometry between metal elements,support and dopants, multiple peptides specific for these discretematerials can be co-expressed within the same phage. Alternatively,precursor salts for the materials can be combined in the reaction at thedesired stochiometry. The techniques for phage propagation andpurification are also well established, robust and scalable.Multi-kilogram amounts of phage can be easily produced, thus assuringstraightforward scale up to large, industrial quantities.

3. Core/Shell Structures

In certain embodiments, nanowires can be grown on a support nanowirethat has no or a different catalytic property. FIG. 8 shows an exemplaryprocess 600 for growing a core/shell structure. Similar to FIG. 7, aphage solution is prepared (block 604), to which a first metal salt anda first anion precursor are sequentially added (blocks 610 and 620) inappropriate conditions to allow for the nucleation and growth of ananowire (M1_(m1)X1_(n1)Z_(p1)) on the phage (block 624). Thereafter, asecond metal salt and a second anion precursor are sequentially added(blocks 630 and 634), under conditions to cause the nucleation andgrowth of a coating of M2_(m2)X2_(n2) Z_(p2) on the nanowireM1_(m1)X1_(n1)Z_(p1) (block 640). Following calcinations, nanowires of acore/shell structure M1_(x1)O_(y1)/M2_(x2)O_(y2) are formed, wherein x1,y1, x2 and y2 are each independently a number from 1 to 100, and p1 andp2 are each independently a number from 0 to 100 (block 644). A furtherstep of impregnation (block 650) produces a nanowire comprising a dopantand comprising a core of M1_(x1)O_(y1) coated with a shell ofM2_(x2)O_(y2). For ease of illustration, FIG. 8 depicts calcinationsprior to doping; however, in certain embodiments doping may be performedprior to calcinations. In some embodiments, M1 is Mg, Al, Ga, Ca or Zr.In certain embodiments of the foregoing, M1 is Mn and M2 is Mg. In otherembodiments, M1 is Mg and M2 is Mn. In other embodiments, M1 is La andM2 is Mg, Ca, Sr, Ba, Zr, Nd, Y, Yb, Eu, Sm or Ce. In other embodiments,M1 is Mg and M2 is La or Nd.

In other embodiments, M1_(x1)O_(y1) comprises La₂O₃ while in otherembodiments M2_(x2)O_(y2) comprises La₂O₃. In other embodiments of theforegoing, M1_(x1)O_(y1) or M2_(x2)O_(y2) further comprises a dopant,wherein the dopant comprises Nd, Mn, Fe, Zr, Sr, Ba, Y or combinationsthereof. Other specific combinations of core/shell nanowires are alsoenvisioned within the scope of the present disclosure.

Thus, one embodiment provides a method for preparing metal oxide, metaloxy-hydroxide, metal oxycarbonate or metal carbonate nanowires in acore/shell structure, the method comprising:

(a) providing a solution that includes a plurality of biologicaltemplates;

(b) introducing a first metal ion and a first anion to the solutionunder conditions and for a time sufficient to allow for nucleation andgrowth of a first nanowire (M1_(m1)X1_(n1) Z_(p1)) on the template;

(c) introducing a second metal ion and optionally a second anion to thesolution under conditions and for a time sufficient to allow fornucleation and growth of a second nanowire (M2_(m2)X2_(n2) Z_(p2)) onthe first nanowire (M1_(m1)X1_(n1) Z_(p1)); and

(d) converting the first nanowire (M1_(m1)X1_(n1) Z_(p1)) and the secondnanowire (M2_(m2)X2_(n2) Z_(p2)) to the respective metal oxide nanowires(M1_(x1)O_(y1)) and (M2_(x2)O_(y2)), the respective metal oxy-hydroxidenanowires (M1_(x1)O_(y1)H_(z1)) and (M2_(x2)O_(y2)OH_(z2)) therespective metal oxycarbonate nanowires (M1_(x1)O_(y1)(CO₃)_(z1)) and(M2_(x2)O_(y2)(CO₃)_(z2)) or the respective metal carbonate nanowires(M1_(x1)(CO₃)_(y1)) and (M2_(x2)(CO₃)_(y2)),

wherein:

M1 and M2 are the same or different and independently selected from ametal element;

X1 and X2 are the same or different and independently hydroxide,carbonate, bicarbonate, phosphate, hydrogenphosphate,dihydrogenphosphate, sulfate, nitrate or oxalate;

Z is O;

n1, m1, n2, m2, x1, y1, z1, x2, y2 and z2 are each independently anumber from 1 to 100; and

p1 and p2 are independently a number from 0 to 100.

In some embodiments, M1 and M2 are the same or different andindependently selected from a metal element from any of Groups 2 through7, lanthanides or actinides

In various embodiments, the biological templates are phages, as definedherein. In further embodiments, the respective metal ion is provided byadding one or more respective metal salts (as described herein) to thesolution. In other embodiments, the respective anions are provided byadding one or more respective anion precursors to the solution. Invarious embodiments, the first metal ion and the first anion can beintroduced to the solution simultaneously or sequentially in any order.Similarly, the second metal ion and optionally the second anion can beintroduced to the solution simultaneously or sequentially in any order.The first and second nanowire are typically converted to a metal oxide,metal oxy-hydroxide, metal oxycarbonate or metal carbonate nanowire in acore/shell structure by calcination.

In yet another embodiment, the method further comprises doping the metaloxide nanowire in a core/shell structure with a dopant.

By varying the nucleation conditions, including the pH of the solution,relative ratio of metal salt precursors and the anion precursors,relative ratios of the precursors and the phage of the syntheticmixture, stable nanowires of diverse compositions and surface propertiescan be prepared.

In certain embodiments, the core nanowire (the first nanowire) is notcatalytically active or less so than the shell nanowire (the secondnanowire), and the core nanowire serve as an intrinsic catalytic supportfor the more active shell nanowire. For example, ZrO₂ may not have highcatalytic activity in an OCM reaction, whereas Sr²⁺ doped La₂O₃ does. AZrO₂ core thus may serve as a support for the catalytic Sr²⁺ doped La₂O₃shell.

In some embodiments, the present disclosure provides a nanowirecomprising a core/shell structure and comprising a ratio of effectivelength to actual length of less than one. In other embodiments, thenanowires having a core/shell structure comprise a ratio of effectivelength to actual length equal to one.

Nanowires in a core/shell arrangement may be prepared in the absence ofa biological template. For example, a nanowire comprising a first metalmay be prepared according to any of the non-template directed methodsdescribed herein. A second metal may then be nucleated or plated ontothe nanowire to form a core/shell nanowire. The first and second metalsmay be the same or different. Other methods for preparing core/shellnanowires in the absence of a biological template are also envisaged.

4. Diversity

As noted above, in some embodiments, the disclosed template-directedsynthesis provides nanowires having diverse compositions and/ormorphologies. This method combines two extremely powerful approaches,evolutionary selection and inorganic synthesis, to produce a library ofnanowire catalysts with a new level of control over materialscomposition, materials surface and crystal structure. These nanowiresprepared by biologically-templated methods take advantage of geneticengineering techniques to enable combinatorial synthesis of robust,active and selective inorganic catalytic polycrystalline nanowires. Withselection, evolution and a combinatorial library with over a hundredbillion sequence possibilities, nanowires having high specificity andproduct conversion yields in catalytic reactions are generated. Thispermits simultaneous optimization the nanowires' catalytic properties ina high-dimensional space.

In various embodiments, the synthetic parameters for nucleating andgrowing nanowires can be manipulated to create nanowires of diversecompositions and morphologies. Typical synthetic parameters include,without limitation, concentration ratios of metal ions and activefunctional groups on the phage; concentration ratios of metal and anions(e.g., hydroxide); incubation time of phage and metal salt; incubationtime of phage and anion; concentration of phage; sequence of addinganion and metal ions; pH; phage sequences; solution temperature in theincubation step and/or growth step; types of metal precursor salt; typesof anion precursor; addition rate, number of additions; the time thatlapses between the additions of the metal salt and anion precursor,including, e.g., simultaneous (zero lapse) or sequential additionsfollowed by respective incubation times for the metal salt and the anionprecursor.

Additional variable synthetic parameters include, growth time once bothmetal and anion are present in the solution; choice of solvents(although water is typically used, certain amounts of alcohol, such asmethanol, ethanol and propanol, can be mixed with water); choice of, orthe number of, metal salts used (e.g., both LaCl₃ and La(NO₃)₃ can beused to provide La³⁺ ions); choice of, or the number of, anionprecursors used (e.g., both NaOH then LiOH can be used to provide thehydroxide); choice of, or the number of, different phage sequences used;the presence or absence of a buffer solution; the different stages ofthe growing step (e.g., nanowires may be precipitated and cleaned andresuspended in a second solution and perform a second growth of the samematerial (thicker core) or different material to form a core/shellstructure.

Thus, libraries of nanowires can be generated with diverse physicalproperties and characteristics such as: composition, e.g., basic metaloxides (M_(x)O_(y)), size, shape, surface morphology, exposed crystalfaces/edge density, crystallinity, dispersion, and stoichiometry andnanowire template physical characteristics including length, width,porosity and pore density. High throughput, combinatorial screeningmethods are then applied to evaluate the catalytic performancecharacteristics of the nanowires (see, e.g., FIG. 2). Based on theseresults, lead target candidates are identified. From these lead targets,further rational modifications to the synthetic designs can be made tocreate nanowires that satisfy certain catalytic performance criteria.This results in further refinement of the nanowire design and materialstructure.

Direct Synthesis of Nanowires

In some embodiments, the nanowires can be synthesized in a solutionphase in the absence of a template. Typically, a hydrothermal or sol gelapproach can be used to create straight (i.e., ratio of effective lengthto actual length equal to one) and substantially single crystallinenanowires. As an example, nanowires comprising a metal oxide can beprepared by (1) forming nanowires of a metal oxide precursor (e.g.,metal hydroxide) in a solution of a metal salt and an anion precursor;(2) isolating the nanowires of the metal oxide precursor; and (3)calcining the nanowires of the metal oxide precursor to providenanowires of a corresponding metal oxide. In other embodiments (forexample MgO nanowires), the synthesis goes through an intermediate whichcan be prepared as a nanowire and then converted into the desiredproduct while maintaining its morphology. Optionally, the nanowirescomprising a metal oxide can be doped according to methods describedherein. Dopant may be incorporated either before or after an optionalcalcination step.

In other certain embodiment, nanowires comprising a core/shell structureare prepared in the absence of a biological template. Such methods mayinclude, for example, preparing a nanowire comprising a first metal andgrowing a shell on the outer surface of this nanowire, wherein the shellcomprises a second metal. The first and second metals may be the same ordifferent.

In other aspects, a core/shell nanowire is prepared in the absence of abiological template. Such methods comprise preparing a nanowirecomprising an inner core and an outer shell, wherein the inner corecomprises a first metal, and the outer shell comprises a second metal,the method comprising:

-   -   a) preparing a first nanowire comprising the first metal; and    -   b) treating the first nanowire with a salt comprising the second        metal.

In some embodiments of the foregoing method, the method furthercomprises addition of an anion precurser to a mixture obtained in stepb). In yet other examples, the first metal and the second metal aredifferent. In yet further embodiments, the salt comprising the secondmetal is a halide or a nitrate. In certain aspects it may beadvantageous to perform one or more sequential additions of the saltcomprising the second metal and an anion precurser. Such sequentialadditions help prevent non-selective precipitation of the second metaland favor conditions wherein the second metal nucleates on the surfaceof the first nanowire to form a shell of the second metal. Furthermore,the first nanowire may be prepared by any method, for example via atemplate directed method (e.g., phage).

As in the template-directed synthesis, the synthetic conditions andparameters of the direct synthesis of nanowires can also be adjusted tocreate diverse compositions and surface morphologies (e.g., crystalfaces) and dopant levels. For example, variable synthetic parametersinclude: concentration ratios of metal and anions (e.g., hydroxide);reaction temperature; reaction time; sequence of adding anion and metalions; pH; types of metal precursor salt; types of anion precursor;number of additions; the time that lapses between the additions of themetal salt and anion precursor, including, e.g., simultaneous (zerolapse) or sequential additions followed by respective incubation timesfor the metal salt and the anion precursor.

In addition, the choice of solvents or surfactants may influence thecrystal growth of the nanowires, thereby generating different nanowiredimensions (including aspect ratios). For example, solvents such asethylene glycol, poly(ethylene glycol), polypropylene glycol andpoly(vinyl pyrrolidone) can serve to passivate the surface of thegrowing nanowires and facilitate a linear growth of the nanowire.

In some embodiments, nanowires can be prepared directly from thecorresponding oxide. For example, metal oxides may be treated withammonium salts to produce nanowires. The ammonium salt comprises saltswith the formula NR₄X, wherein each R is independently selected from H,alkyl, alkenyl, alkynyls and aryl (e.g., methyl, ethyl, propyl,isopropyl, butyl, tert-butyl, pentenyl, cyclohexyl, phenyl, tolyl,benzyl, hexynyl, octyl, octenyl, octynyl, dodecyl, cetyl, oleyl,stearyl, and the like) and X is an anion, for example halide, phosphate,hydrogenphosphate, dihydrogenphosphate, metatungstate, tungstate,molybdate, bicarbonate sulfate, nitrate or acetate. In otherembodiments, X is phosphate, hydrogenphosphate, dihydrogenphosphate,metatungstate, tungstate, molybdate, bicarbonate sulfate, nitrate oracetate. Examples of the ammonium salt comprise ammonium chloride,dimethylammonium chloride, methylammonium chloride, ammonium acetate,ammonium nitrate, dimethylammonium nitrate, methylammonium nitrate,cetyl trimethylammonium bromide (CTAB) and the like. The methods mayinclude treating the metal oxide and ammonium salts at temperaturesranging from room temperature (or lower) to reflux temperature in anappropriate solvent (e.g., water) for a time sufficient to produce thenanowires. Certain embodiments comprise heating the metal oxide andammonium salt under hydrothermal conditions at temperatures ranging fromreflux temperature (at atmospheric pressure) to 300° C. Such embodimentsfind particular utility in the context of lanthanide oxides, for exampleLa₂O₃, are particularly useful since the procedure is quite simple andeconomically efficient. Nanowires comprising two or more metals and/ordopants may also be prepared according to these methods. Accordingly, insome embodiments at least one of the metal compounds is an oxide of alanthanide element. Such methods are described in more detail in theexamples.

Accordingly, in one embodiment the present disclosure provides a methodfor preparing a nanowire in the absence of a biological template, themethod comprising treating at least one metal compound with an ammoniumsalt. In certain embodiments, nanowires comprising more than one type ofmetal and/or one or more dopants can be prepared by such methods. Forexample, in one embodiment the method comprises treating two or moredifferent metal compounds with an ammonium salt and the nanowirecomprises two or more different metals. The nanowire may comprise amixed metal oxide, metal oxyhalide, metal oxynitrate or metal sulfate.

In some other embodiments of the foregoing, the ammonium salt is in theform of NR₄X, wherein each R is independently selected from H, alkyl,alkenyl, and aryl and X is a halide, sulfate, nitrate or acetate.Examples of the ammonium salt comprise ammonium chloride,dimethylammonium chloride, methylammonium chloride, ammonium acetate,ammonium nitrate, dimethylammonium nitrate, methylammonium nitrate. Insome other embodiments, each R is independently methyl, ethyl, propyl,isopropyl, butyl, tert-butyl, pentenyl, cyclohexyl, phenyl, tolyl,benzyl, hexynyl, octyl, octenyl, octynyl, dodecyl, cetyl, oleyl orstearyl. In yet other embodiments, the ammonium salt is contacted withthe metal compound in solution or in the solid state.

In certain embodiments, the method is useful for incorporation of one ormore doping elements into a nanowire. For example, the method maycomprise treating at least one metal compound with a halide in thepresence of at least one doping element, and the nanowire comprises atleast one doping element. In some aspects, the at least one dopingelement is present in the nanowire in an atomic percent ranging from 0.1to 50 at %.

Other methods for preparation of nanowires in the absence of abiological template include preparing a metal hydroxide gel by reactionof at least one metal salt and a base. In some embodiments the metalsalt comprises a lanthanide halide and the resulting nanowire comprisesa lanthanide oxide (e.g., La₂O₃). For example, the method may furthercomprise aging the gel, heating the gel or combinations thereof. Agingor heating the gel includes aging at temperatures ranging from roomtemperature (e.g., 20° C.) or below to reflux for a time sufficient toproduce the desired nanowires. In certain other embodiments, the methodcomprises reaction of two or more different metal salts, and thenanowire comprises two or more different metals. In yet otherembodiments, the method comprises reaction of two or more differentmetal salts, and the product comprises nanowires of two or moredifferent metals.

Doping elements may also be incorporated by using the hydroxide gelmethod described above, further comprising addition of at least onedoping element to the hydroxide gel, and wherein the nanowire comprisesthe at least one doping element. For example, the at least one dopingelement may be present in the nanowire in an atomic percent ranging from0.1 to 50 at %.

In some embodiments, metal oxide nanowires can be prepared by mixing ametal salt solution and an anion precursor so that a gel of a metaloxide precursor is formed. This method can work for cases where thetypical morphology of the metal oxide precursor is a nanowire. The gelis thermally treated so that crystalline nanowires of the metal oxideprecursor are formed. The metal oxide precursor nanowires are convertedto metal oxide nanowires by calcination, further chemical reaction orcombinations thereof. In some embodiments, this method is useful forlanthanides and group 3 elements. In some embodiments, the thermaltreatment of the gel is hydrothermal (or solvothermal) at temperaturesabove the boiling point (at standard pressure) of the reaction mixtureand at pressures above ambient pressure, in other embodiments it's doneat ambient pressure and at temperatures equal to or below the boilingpoint of the reaction mixture. In some embodiments the thermal treatmentis done under reflux conditions at temperatures equal to the boilingpoint of the mixture. In some specific embodiments the anion precursoris a hydroxide, e.g. Ammonium hydroxide, sodium hydroxide, lithiumhydroxide, tetramethyl ammonium hydroxide, and the like. In some otherspecific embodiments the metal salt is LnCl₃ (Ln=Lanthanide), in otherembodiment the metal salt is Ln(NO₃)₃. In yet other embodiments, themetal salt is YCl₃, ScCl₃, Y(NO₃)₃, Sc(NO₃)₃. In some other embodiments,the metal precursor solution is an aqueous solution. In otherembodiments, the thermal treatment is done at T=100° C. under refluxconditions.

This method can be used to make mixed metal oxide nanowires, by mixingat least two metal salt solutions and an anion precursor so that a mixedoxide precursor gel is formed. In such cases, the first metal may be alathanide or a group 3 element, and the other metals can be from othergroups, including groups 1-14 and lanthanides.

In some different embodiments, metal oxide nanowires can be prepared ina similar way as described above by mixing a metal salt solution and ananion precursor so that a gel of a metal hydroxide precursor is formed.This method works for cases where the typical morphology of the metalhydroxide precursor is a nanowire. The gel is treated so thatcrystalline nanowires of the metal hydroxide precursor are formed. Themetal hydroxide precursor nanowires are converted to metal hydroxidenanowires by base treatment and finally converted to metal oxidenanowires by calcination. In some embodiments, this method may beespecially applicable for group 2 elements, for example Mg. In somespecific embodiments, the gel treatment is a thermal treatment attemperatures in the range 50-100° C. followed by hydrothermal treatment.In other embodiments, the gel treatment is an aging step. In someembodiments, the aging step takes at least one day. In some specificembodiments, the metal salt solution is a concentrated metal chlorideaqueous solution and the anion precursor is the metal oxide. In somemore specific embodiments, the metal is Mg. In certain embodiments ofthe above, these methods can be used to make mixed metal oxidenanowires. In these embodiments, the first metal is Mg and the othermetal can be any other metal of groups 1-14+Ln.

Catalytic Reactions

The present disclosure provides for the use of catalytic nanowires ascatalysts in catalytic reactions and related methods. In someembodiments, the catalytic reaction is any of the reactions describedherein. The morphology and composition of the catalytic nanowires is notlimited, and the nanowires may be prepared by any method. For examplethe nanowires may have a bent morphology or a straight morphology andmay have any molecular composition. In some embodiments, the nanowireshave better catalytic properties than a corresponding bulk catalyst(i.e., a catalyst having the same chemical composition as the nanowire,but prepared from bulk material). In some embodiments, the nanowirehaving better catalytic properties than a corresponding bulk catalysthas a ratio of effective length to actual length equal to one. In otherembodiments, the nanowire having better catalytic properties than acorresponding bulk catalyst has a ratio of effective length to actuallength of less than one. In other embodiments, the nanowire havingbetter catalytic properties than a corresponding bulk catalyst comprisesone or more elements from Groups 1 through 7, lanthanides or actinides.

Nanowires may be useful in any number of reactions catalyzed by aheterogeneous catalyst. Examples of reactions wherein nanowires havingcatalytic activity may be employed are disclosed in Farrauto andBartholomew, “Fundamentals of Industrial Catalytic Processes” BlackieAcademic and Professional, first edition, 1997, which is herebyincorporated in its entirety. Other non-limiting examples of reactionswherein nanowires having catalytic activity may be employed include: theoxidative coupling of methane (OCM) to ethane and ethylene; oxidativedehydrogenation (ODH) of alkanes to the corresponding alkenes, forexample oxidative dehydrogenation of ethane or propane to ethylene orpropylene, respectively; selective oxidation of alkanes, alkenes, andalkynes; oxidation of CO, dry reforming of methane, selective oxidationof aromatics; Fischer-Tropsch, hydrocarbon cracking; combustion ofhydrocarbons and the like. Reactions catalyzed by the disclosednanowires are discussed in more detail below.

The nanowires are generally useful as catalysts in methods forconverting a first carbon-containing compound (e.g., a hydrocarbon, COor CO₂) to a second carbon-containing compound. In some embodiments themethods comprise contacting a nanowire, or material comprising the same,with a gas comprising a first carbon-containing compound and an oxidantto produce a carbon-containing compound. In some embodiments, the firstcarbon-containing compound is a hydrocarbon, CO, CO₂, methane, ethane,propane, hexane, cyclohexane, octane or combinations thereof. In otherembodiments, the second carbon-containing compound is a hydrocarbon, CO,CO₂, ethane, ethylene, propane, propylene, hexane, hexene, cyclohexane,cyclohexene, bicyclohexane, octane, octene or hexadecane. In someembodiments, the oxidant is oxygen, ozone, nitrous oxide, nitric oxide,carbon dioxide, water or combinations thereof.

In other embodiments of the foregoing, the method for conversion of afirst carbon-containing compound to a second carbon-containing compoundis performed at a temperature below 100° C., below 200° C., below 300°C., below 400° C., below 500° C., below 600° C., below 700° C., below800° C., below 900° C. or below 1000° C. In other embodiments, themethod for conversion of a first carbon-containing compound to a secondcarbon-containing compound is performed at a pressure above 0.5 ATM,above 1 ATM, above 2 ATM, above 5 ATM, above 10 ATM, above 25 ATM orabove 50 ATM.

The catalytic reactions described herein can be performed using standardlaboratory equipment known to those of skill in the art, for example asdescribed in U.S. Pat. No. 6,350,716, which is incorporated herein inits entirety.

As noted above, the nanowires disclosed herein have better catalyticactivity than a corresponding bulk catalyst. In some embodiments, theselectivity, yield, conversion, or combinations thereof, of a reactioncatalyzed by the nanowires is better than the selectivity, yield,conversion, or combinations thereof, of the same reaction catalyzed by acorresponding bulk catalyst under the same conditions. For example, insome embodiments, the nanowire possesses a catalytic activity such thatconversion of reactant to product in a reaction catalyzed by thenanowire is greater than at least 1.1 times, greater than at least 1.25times, greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times or greater than at least 4.0 times theconversion of reactant to product in the same reaction catalyzed by acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire.

In other embodiments, the nanowire possesses a catalytic activity suchthat selectivity for product in a reaction catalyzed by the nanowire isgreater than at least 1.1 times, greater than at least 1.25 times,greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times, or greater than at least 4.0 times theselectivity for product in the same reaction under the same conditionsbut catalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In yet other embodiments, the nanowire possesses a catalytic activitysuch that yield of product in a reaction catalyzed by the nanowire isgreater than at least 1.1 times, greater than at least 1.25 times,greater than at least 1.5 times, greater than at least 2.0 times,greater than at least 3.0 times, or greater than at least 4.0 times theyield of product in the same reaction under the same conditions butcatalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In yet other embodiments, the nanowire possesses a catalytic activitysuch that activation temperature of a reaction catalyzed by the nanowireis at least 25° C. lower, at least 50° C. lower, at least 75° C. lower,or at least 100° C. lower than the temperature of the same reactionunder the same conditions but catalyzed by a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire.

In certain reactions (e.g., OCM), production of unwanted oxides ofcarbon (e.g., CO and CO₂) is a problem that reduces overall yield ofdesired product and results in an environmental liability. Accordingly,in one embodiment the present disclosure addresses this problem andprovides nanowires with a catalytic activity such that the selectivityfor CO and/or CO₂ in a reaction catalyzed by the nanowires is less thanthe selectivity for CO and/or CO₂ in the same reaction under the sameconditions but catalyzed by a corresponding bulk catalyst. Accordingly,in one embodiment, the present disclosure provides a nanowire whichpossesses a catalytic activity such that selectivity for CO_(x), whereinx is 1 or 2, in a reaction catalyzed by the nanowire is less than atleast 0.9 times, less than at least 0.8 times, less than at least 0.5times, less than at least 0.2 times or less than at least 0.1 times theselectivity for CO_(x) in the same reaction under the same conditionsbut catalyzed by a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In some embodiments, the absolute selectivity, yield, conversion, orcombinations thereof, of a reaction catalyzed by the nanowires disclosedherein is better than the absolute selectivity, yield, conversion, orcombinations thereof, of the same reaction under the same conditions butcatalyzed by a corresponding bulk catalyst. For example, in someembodiments the yield of product in a reaction catalyzed by thenanowires is greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%. In other embodiments, theselectivity for product in a reaction catalyzed by the nanowires isgreater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%. In other embodiments, the conversion of reactant toproduct in a reaction catalyzed by the nanowires is greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In addition to the improved catalytic performance of the disclosednanowires, the morphology of the nanowires is expected to provide forimproved mixing properties for the nanowires compared to standardcolloidal (e.g., bulk) catalyst materials. The improved mixingproperties are expected to improve the performance of any number ofcatalytic reactions, for example, in the area of transformation of heavyhydrocarbons where transport and mixing phenomena are known to influencethe catalytic activity. In other reactions, the shape of the nanowiresis expected to provide for good blending, reduce settling, and providefor facile separation of any solid material.

In some other chemical reactions, the nanowires are useful forabsorption and/or incorporation of a reactant used in chemical looping.For example, the nanowires find utility as NO_(x) traps, in unmixedcombustion schemes, as oxygen storage materials, as CO₂ sorptionmaterials (e.g., cyclic reforming with high H₂ output) and in schemesfor conversion of water to H₂.

1. Oxidative Coupling of Methane (OCM)

As noted above, the present disclosure provides nanowires havingcatalytic activity and related approaches to nanowire design andpreparation for improving the yield, selectivity and/or conversion ofany number of catalyzed reactions, including the OCM reaction. Asmentioned above, there exists a tremendous need for catalyst technologycapable of addressing the conversion of methane into high valuechemicals (e.g., ethylene and products prepared therefrom) using adirect route that does not go through syngas. Accomplishing this taskwill dramatically impact and redefine a non-petroleum based pathway forfeedstock manufacturing and liquid fuel production yielding reductionsin GHG emissions, as well as providing new fuel sources.

Ethylene has the largest carbon footprint compared to all industrialchemical products in part due to the large total volume consumed into awide range of downstream important industrial products includingplastics, surfactants and pharmaceuticals. In 2008, worldwide ethyleneproduction exceeded 120 M metric tons while growing at a robust rate of4% per year. The United States represents the largest single producer at28% of the world capacity. Ethylene is primarily manufactured from hightemperature cracking of naphtha (e.g., oil) or ethane that is separatedfrom natural gas. The true measurement of the carbon footprint can bedifficult as it depends on factors such as the feedstock and theallocation as several products are made and separated during the sameprocess. However, some general estimates can be made based on publisheddata.

Cracking consumes a significant portion (about 65%) of the total energyused in ethylene production and the remainder is for separations usinglow temperature distillation and compression. The total tons of CO₂emission per ton of ethylene are estimated at between 0.9 to 1.2 fromethane cracking and 1 to 2 from naphtha cracking. Roughly, 60% ofethylene produced is from naphtha, 35% from ethane and 5% from otherssources (Ren, T.; Patel, M. Res. Conserv. Recycl. 53:513, 2009).Therefore, based on median averages, an estimated amount of CO₂emissions from the cracking process is 114M tons per year (based on 120Mtons produced). Separations would then account for an additional 61Mtons CO₂ per year.

Nanowires provide an alternative to the need for the energy intensivecracking step. Additionally, because of the high selectivity of thenanowires, downstream separations are dramatically simplified, ascompared to cracking which yields a wide range of hydrocarbon products.The reaction is also exothermic so it can proceed via an autothermalprocess mechanism. Overall, it is estimated that up to a potential 75%reduction in CO₂ emission compared to conventional methods could beachieved. This would equate to a reduction of one billion tons of CO₂over a ten-year period and would save over 1M barrels of oil per day.

The nanowires also permit converting ethylene into liquid fuels such asgasoline or diesel, given ethylene's high reactivity and numerouspublications demonstrating high yield reactions, in the lab setting,from ethylene to gasoline and diesel. On a life cycle basis from well towheel, recent analysis of methane to liquid (MTL) using F-T processderived gasoline and diesel fuels has shown an emission profileapproximately 20% greater to that of petroleum based production (basedon a worst case scenario) (Jaramillo, P., Griffin, M., Matthews, S.,Env. Sci. Tech 42:7559, 2008). In the model, the CO₂ contribution fromplant energy was a dominating factor at 60%. Thus, replacement of thecracking and F-T process would be expected to provide a notablereduction in net emissions, and could be produced at lower CO₂ emissionsthan petroleum based production.

Furthermore, a considerable portion of natural gas is found in regionsthat are remote from markets or pipelines. Most of this gas is flared,re-circulated back into oil reservoirs, or vented given its low economicvalue. The World Bank estimates flaring adds 400M metric tons of CO₂ tothe atmosphere each year as well as contributing to methane emissions.The nanowires of this disclosure also provide economic and environmentalincentive to stop flaring. Also, the conversion of methane to fuel hasseveral environmental advantages over petroleum-derived fuel. Naturalgas is the cleanest of all fossil fuels, and it does not contain anumber of impurities such as mercury and other heavy metals found inoil. Additionally, contaminants including sulfur are also easilyseparated from the initial natural gas stream. The resulting fuels burnmuch cleaner with no measurable toxic pollutants and provide loweremissions than conventional diesel and gasoline in use today.

In view of its wide range of applications, the nanowires of thisdisclosure can be used to not only selectively activate alkanes, butalso to activate other classes of inert unreactive bonds, such as C—F,C—Cl or C—O bonds. This has importance, for example, in the destructionof man-made environmental toxins such as CFCs, PCBs, dioxins and otherpollutants. Accordingly, while the invention is described in greaterdetail below in the context of the OCM reaction and other the otherreactions described herein, the nanowire catalysts are not in any waylimited to this particular reaction.

The selective, catalytic oxidative coupling of methane to ethylene (i.e.the OCM reaction) is shown by the following reaction (1):2CH₄+O₂→CH₂CH₂+2 H₂O  (1)This reaction is exothermic (Heat of Reaction −67 kcals/mole) andusually occurs at very high temperatures (>700° C.). During thisreaction, it is believed that the methane (CH₄) is first oxidativelycoupled into ethane (C₂H₆), and subsequently the ethane (C₂H₆) isoxidatively dehydrogenated into ethylene (C₂H₄). Because of the hightemperatures used in the reaction, it has been suggested that the ethaneis produced mainly by the coupling in the gas phase of thesurface-generated methyl (CH₃) radicals. Reactive metal oxides (oxygentype ions) are apparently required for the activation of CH₄ to producethe CH₃ radicals. The yield of C₂H₄ and C₂H₆ is limited by furtherreactions in the gas phase and to some extent on the catalyst surface. Afew of the possible reactions that occur during the oxidation of methaneare shown below as reactions (2) through (8):CH₄→CH₃ radical  (2)CH₃ radical→C₂H₆  (3)CH₃ radical+2.5 O₂→CO₂+1.5 H₂O  (4)C₂H₆→C₂H₄+H₂  (5)C₂H₆+0.5 O₂→C₂H₄+H₂O  (6)C₂H₄+3 O₂→2CO₂+2H₂O  (7)CH₃ radical+C_(x)H_(y)+O₂→Higher HC's−Oxidation/CO₂+H₂O  (8)

With conventional heterogeneous catalysts and reactor systems, thereported performance is generally limited to <25% CH₄ conversion at <80%combined C₂ selectivity, with the performance characteristics of highselectivity at low conversion, or the low selectivity at highconversion. In contrast, the nanowires of this disclosure are highlyactive and can optionally operate at a much lower temperature. In oneembodiment, the nanowires disclosed herein enable efficient conversionof methane to ethylene in the OCM reaction at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires disclosed herein enable efficientconversion (i.e., high yield, conversion, and/or selectivity) of methaneto ethylene at temperatures of less than 900° C., less than 800° C.,less than 700° C., less than 600° C., or less than 500° C. In otherembodiments, the use of staged oxygen addition, designed heatmanagement, rapid quench and/or advanced separations may also beemployed.

Accordingly, one embodiment of the present disclosure is a method forthe preparation of ethane and/or ethylene, the method comprisingconverting methane to ethane and/or ethylene in the presence of acatalytic material, wherein the catalytic material comprises at leastone catalytic nanowire as disclosed herein.

Accordingly, in one embodiment a stable, very active, high surface area,multifunctional nanowire catalyst is disclosed having active sites thatare isolated and precisely engineered with the catalytically activemetal centers/sites in the desired proximity (see, e.g., FIG. 1).

The exothermic heats of reaction (free energy) follow the order ofreactions depicted above and, because of the proximity of the activesites, will mechanistically favor ethylene formation while minimizingcomplete oxidation reactions that form CO and CO₂. Representativenanowire compositions useful for the OCM reaction include, but are notlimited to: highly basic oxides selected from the early members of theLanthanide oxide series; Group 1 or 2 ions supported on basic oxides,such as Li/MgO, Ba/MgO and Sr/La₂O₃; and single or mixed transitionmetal oxides, such as VO_(x) and Re/Ru that may also contain Group 1ions. Other nanowire compositions useful for the OCM reaction compriseany of the compositions disclosed herein, for example MgO, La₂O₃,Na₂WO₄, Mn₂O₃, Mn₃O₄, Mg₆MnO₈, Zr₂Mo₂O₈, NaMnO₄, Mn₂O₃/Na₂WO₄,Mn₃O₄/Na₂WO₄ or Na/MnO₄/MgO, Mn/WO4, Nd₂O₃, Sm₂O₃, Eu₂O₃ or combinationsthereof. Activating promoters (i.e., dopants), such as chlorides,nitrates and sulfates, or any of the dopants described above may also beemployed.

As noted above, the presently disclosed nanowires comprise a catalyticperformance better than corresponding bulk catalysts, for example in oneembodiment the catalytic performance of the nanowires in the OCMreaction is better than the catalytic performance of a correspondingbulk catalyst. In this regard, various performance criteria may definethe “catalytic performance” of the catalysts in the OCM (and otherreactions). In one embodiment, catalytic performance is defined by C2selectivity in the OCM reaction, and the C2 selectivity of the nanowiresin the OCM reactionis >5%, >10%, >15%, >20%, >25%, >30%, >35%, >40%, >45%, >50%, >55%, >60%, >65%, >70%, >75%or >80%.

Other important performance parameters used to measure the nanowires'catalytic performance in the OCM reaction are selected from single passmethane conversion percentage (i.e., the percent of methane converted ona single pass over the catalyst or catalytic bed, etc.), reaction inletgas temperature, reaction operating temperature, total reactionpressure, methane partial pressure, gas-hour space velocity (GHSV), O₂source, catalyst stability and ethylene to ethane ratio. In certainembodiments, improved catalytic performance is defined in terms of thenanowires' improved performance (relative to a corresponding bulkcatalyst) with respect to at least one of the foregoing performanceparameters.

The reaction inlet gas temperature in an OCM reaction catalyzed by thedisclosed nanowires can generally be maintained at a lower temperature,while maintaining better performance characteristics (e.g., conversion,C2 yield, C2 selectivity and the like) compared to the same reactioncatalyzed by a corresponding bulk catalyst under the same reactionconditions. In certain embodiments, the inlet gas temperature in an OCMreaction catalyzed by the disclosed nanowires is <700° C., <675° C.,<650° C., <625° C., <600° C., <593° C., <580° C., <570° C., <560° C.,<550° C., <540° C., <530° C., <520° C., <510° C., <500° C., <490° C.,<480° C. or even <470° C.

The reaction operating temperature in an OCM reaction catalyzed by thedisclosed nanowires can generally be maintained at a lower temperature,while maintaining better performance characteristics compared to thesame reaction catalyzed by a corresponding bulk catalyst under the samereaction conditions. In certain embodiments, the reaction operatingtemperature in an OCM reaction catalyzed by the disclosed nanowires is<700° C., <675° C., <650° C., <625° C., <600° C., <593° C., <580° C.,<570° C., <560° C., <550° C., <540° C., <530° C., <520° C., <510° C.,<500° C., <490° C., <480° C., <470° C.

The single pass methane conversion in an OCM reaction catalyzed by thenanowires is also generally better compared to the single pass methaneconversion in the same reaction catalyzed by a corresponding bulkcatalyst under the same reaction conditions. For single pass methaneconversion it ispreferably >5%, >10%, >15%, >20%, >25%, >30%, >35%, >40%, >45%, >50%, >55%, >60%, >65%, >70%, >75%,>80%.

In certain embodiments, the total reaction pressure in an OCM reactioncatalyzed by the nanowires is >1 atm, >1.1 atm, >1.2 atm, >1.3 atm, >1.4atm, >1.5 atm, >1.6 atm, >1.7 atm, >1.8 atm, >1.9 atm, >2 atm, >2.1atm, >2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm, >2.5 atm, >2.6 atm, >2.7atm, >2.8 atm, >2.9 atm, >3.0 atm, >3.5 atm, >4.0 atm, >4.5 atm, >5.0atm, >5.5 atm, >6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm, >8.0 atm, >8.5atm, >9.0 atm, >10.0 atm, >11.0 atm, >12.0 atm, >13.0 atm, >14.0atm, >15.0 atm, >16.0 atm, >17.0 atm, >18.0 atm, >19.0 atm or >20.0 atm.

In certain other embodiments, the total reaction pressure in an OCMreaction catalyzed by the nanowires ranges from about 1 atm to about 10atm, from about 1 atm to about 7 atm, from about 1 atm to about 5 atm,from about 1 atm to about 3 atm or from about 1 atm to about 2 atm.

In some embodiments, the methane partial pressure in an OCM reactioncatalyzed by the nanowires is >0.3 atm, >0.4 atm, >0.5 atm, >0.6atm, >0.7 atm, >0.8 atm, >0.9 atm, >1 atm, >1.1 atm, >1.2 atm, >1.3atm, >1.4 atm, >1.5 atm, >1.6 atm, >1.7 atm, >1.8 atm, >1.9 atm, >2.0atm, >2.1 atm, >2.2 atm, >2.3 atm, >2.4 atm, >2.5 atm, >2.6 atm, >2.7atm, >2.8 atm, >2.9 atm, >3.0 atm, >3.5 atm, >4.0 atm, >4.5 atm, >5.0atm, >5.5 atm, >6.0 atm, >6.5 atm, >7.0 atm, >7.5 atm, >8.0 atm, >8.5atm, >9.0 atm, >10.0 atm, >11.0 atm, >12.0 atm, >13.0 atm, >14.0atm, >15.0 atm, >16.0 atm, >17.0 atm, >18.0 atm, >19.0 atm or >20.0 atm.

In some embodiments, the GSHV in an OCM reaction catalyzed by thenanowiresis >20,000/hr, >50,000/hr, >75,000/hr, >100,000/hr, >120,000/hr, >130,000/hr, >150,000/hr, >200,000/hr, >250,000/hr, >300,000/hr, >350,000/hr, >400,000/hr, >450,000/hr, >500,000/hr, >750,000/hr, >1,000,000/hr, >2,000,000/hr, >3,000,000/hr,>4,000,000/hr.

In contrast to other OCM reactions, the present inventors havediscovered that OCM reactions catalyzed by the disclosed nanowires canbe performed (and still maintain high C2 yield, C2 selectivity,conversion, etc.) using O₂ sources other than pure O₂. For example, insome embodiments the O₂ source in an OCM reaction catalyzed by thedisclosed nanowires is air, oxygen enriched air, pure oxygen, oxygendiluted with nitrogen (or another inert gas) or oxygen diluted with CO₂.In certain embodiments, the O₂ source is O₂ dilutedby >99%, >98%, >97%, >96%, >95%, >94%, >93%, >92%, >91%, >90%, >85%, >80%, >75%, >70%, >65%, >60%, >55%, >50%, >45%, >35%, >30%, >25%, >40%, >20%, >15%, >10%, >9%, >8%, >7%, >6%, >5%, >4%, >3%, >2%or >1% with CO₂ or an inert gas, for example nitrogen.

The disclosed nanowires are also very stable under conditions requiredto perform any number of catalytic reactions, for example the OCMreaction. The stability of the nanowires is defined as the length oftime a catalyst will maintain its catalytic performance without asignificant decrease in performance (e.g., adecrease >20%, >15%, >10%, >5%, or greater than 1% in C2 yield, C2selectivity or conversion, etc.). In some embodiments, the nanowireshave stability under conditions required for the OCM reaction of >1hr, >5 hrs, >10 hrs, >20 hrs, >50 hrs, >80 hrs, >90 hrs, >100 hrs, >150hrs, >200 hrs, >250 hrs, >300 hrs, >350 hrs, >400 hrs, >450 hrs, >500hrs, >550 hrs, >600 hrs, >650 hrs, >700 hrs, >750 hrs, >800 hrs, >850hrs, >900 hrs, >950 hrs, >1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000hrs, >5,000 hrs, >6,000 hrs, >7,000 hrs, >8,000 hrs, >9,000 hrs, >10,000hrs, >11,000 hrs, >12,000 hrs, >13,000 hrs, >14,000 hrs, >15,000hrs, >16,000 hrs, >17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1yrs, >2 yrs, >3 yrs, >4 yrs or >5 yrs.

In some embodiments, the ratio of ethylene to ethane in an OCM reactioncatalyzed by the nanowires is better than the ratio of ethylene toethane in an OCM reaction catalyzed by a corresponding bulk catalystunder the same conditions. In some embodiments, the ratio of ethylene toethane in an OCM reaction catalyzed by the nanowiresis >0.3, >0.4, >0.5, >0.6, >0.7, >0.8, >0.9, >1, >1.1, >1.2, >1.3, >1.4, >1.5, >1.6, >1.7, >1.8, >1.9, >2.0, >2.1, >2.2, >2.3, >2.4, >2.5, >2.6, >2.7, >2.8, >2.9, >3.0, >3.5, >4.0, >4.5, >5.0, >5.5, >6.0, >6.5, >7.0, >7.5, >8.0, >8.5, >9.0, >9.5,>10.0.

As noted above, the OCM reaction employing known bulk catalysts suffersfrom poor yield, selectivity, or conversion. In contrast to acorresponding bulk catalyst, Applicants have found that certainnanowires, for example the exemplary nanowires disclosed herein, possesa catalytic activity in the OCM reaction such that the yield,selectivity, and/or conversion is better than when the OCM reaction iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that theconversion of methane to ethylene in the oxidative coupling of methanereaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of methane to ethylenecompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion ofmethane to ethylene in an OCM reaction catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of ethylene in the oxidativecoupling of methane reaction is greater than at least 1.1 times, 1.25times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the yield ofethylene compared to the same reaction under the same conditions butperformed with a catalyst prepared from bulk material having the samechemical composition as the nanowire. In some embodiments the yield ofethylene in an OCM reaction catalyzed by the nanowire is greater than10%, greater than 20%, greater than 30%, greater than 50%, greater than75%, or greater than 90%.

As noted above, the OCM reaction employing known bulk catalysts suffersfrom poor yield, selectivity, or conversion. In contrast to acorresponding bulk catalyst, Applicants have found that certainnanowires, for example the exemplary nanowires disclosed herein, possesa catalytic activity in the OCM reaction such that the yield,selectivity, and/or conversion is better than when the OCM reaction iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that theconversion of methane in the oxidative coupling of methane reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the conversion of methane compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the conversion of methane in an OCMreaction catalyzed by the nanowire is greater than 10%, greater than20%, greater than 30%, greater than 50%, greater than 75%, or greaterthan 90%. In some embodiments the conversion of methane is determinedwhen the catalyst is employed as a heterogenous catalyst in theoxidative coupling of methane at a temperature of 750° C. or less, 700°C. or less, 650° C. or less or even 600° C. or less. The conversion ofmethane may also be determined based on a single pass of a gascomprising methane over the catalyst or may be determined based onmultiple passes over the catalyst.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the C2 yield in the oxidative coupling ofmethane reaction is greater than at least 1.1 times, 1.25 times, 1.50times, 2.0 times, 3.0 times, or 4.0 times the C2 yield compared to thesame reaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In some embodiments the C2 yield in an OCM reaction catalyzedby the nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%. In someembodiments the C2 yield is determined when the catalyst is employed asa heterogenous catalyst in the oxidative coupling of methane at atemperature of 750° C. or less, 700° C. or less, 650° C. or less or even600° C. or less. The C2 yield may also be determined based on a singlepass of a gas comprising methane over the catalyst or may be determinedbased on multiple passes over the catalyst.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the OCM reaction such that the nanowire has thesame catalytic activity (i.e., same selectivity, conversion or yield),but at a lower temperature, compared a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire. In someembodiments the catalytic activity of the nanowires in the OCM reactionis the same as the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 20° C. less. In some embodiments the catalyticactivity of the nanowires in the OCM reaction is the same as thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 50° C. less. In some embodiments the catalytic activity of thenanowires in the OCM reaction is the same as the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in theOCM reaction is the same as the catalytic activity of a catalystprepared from bulk material having the same chemical composition as thenanowire, but at a temperature of at least 200° C. less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO or CO₂ in theoxidative coupling of methane reaction is less than at least 0.9 times,0.8 times, 0.5 times, 0.2 times, or 0.1 times the selectivity for CO orCO₂ compared to the same reaction under the same conditions butperformed with a catalyst prepared from bulk material having the samechemical composition as the nanowire.

In some other embodiments, a method for converting methane into ethylenecomprising use of catalyst mixture comprising two or more catalysts isprovided. For example, the catalyst mixture may be a mixture of acatalyst having good OCM activity and a catalyst having good ODHactivity. Such catalyst mixture are described in more detail above.

Typically, the OCM reaction is run in a mixture of oxygen and nitrogenor other inert gas. Such gasses are expensive and increase the overallproduction costs associated with preparation of ethylene or ethane frommethane. However, the present inventors have now discovered that suchexpensive gases are not required and high yield, conversion,selectivity, etc. can be obtained when air is used as the gas mixtureinstead of pre-packaged and purified sources of oxygen and other gases.Accordingly, in one embodiment the disclosure provides a method forperforming the OCM reaction in air.

In addition to air or O₂ gas, the presently disclosed nanowires andassociated methods provide for use of other sources of oxygen in the OCMreaction. In this respect, an alternate source of oxygen such a CO₂,H₂O, SO₂ or SO₃ may be used either in place of, or in addition to, airor oxygen as the oxygen source. Such methods have the potential toincrease the efficiency of the OCM reaction, for example by consuming areaction byproduct (e.g., CO₂ or H₂O) and controlling the OCM exothermas described below.

As noted above, in the OCM reaction, methane is oxidatively converted tomethyl radicals, which are then coupled to form ethane, which issubsequently oxidized to ethylene. In traditional OCM reactions, theoxidation agent for both the methyl radical formation and the ethaneoxidation to ethylene is oxygen. In order to minimize full oxidation ofmethane or ethane to carbon dioxide, i.e. maximize C2 selectivity, themethane to oxygen ratio is generally kept at 4 (i.e. full conversion ofmethane into methyl radicals) or above. As a result, the OCM reaction istypically oxygen limited and thus the oxygen concentration in theeffluent is zero.

Accordingly, in one embodiment the present disclosure provides a methodfor increasing the methane conversion and increasing, or in someembodiments, not reducing, the C2 selectivity in an OCM reaction. Thedisclosed methods include adding to a traditional OCM catalyst anotherOCM catalyst that uses an oxygen source other than molecular oxygen. Insome embodiments, the alternate oxygen source is CO₂, H₂O, SO₂, SO₃ orcombinations thereof. For example in some embodiments, the alternateoxygen source is CO₂. In other embodiments the alternate oxygen sourceis H₂O.

Because C2 selectivity is typically between 50% and 80% in the OCMreaction, OCM typically produces significant amounts of CO₂ as abyproduct (CO₂ selectivity can typically range from 20-50%).Additionally, H₂O is produced in copious amounts, regardless of the C2selectivity. Therefore both CO₂ and H₂O would are attractive oxygensources for OCM in an O₂ depleted environment.

Accordingly, one embodiment of the present disclosure provides acatalyst (and related methods for use thereof) which is catalytic in theOCM reaction and which uses CO₂, H₂O, SO₂, SO₃ or another alternativeoxygen source or combinations thereof as a source of oxygen. Otherembodiments, provide a catalytic material comprising two or morecatalysts, wherein the catalytic material comprises at least onecatalyst which is catalytic in the OCM reaction and uses O₂ for at leastone oxygen source and at least one catalysts which is catalytic in theOCM reaction and uses at least of CO₂, H₂O, SO₂, SO₃, NO, NO₂, NO₃ oranother alternative oxygen source. Methods for performing the OCMreaction with such catalytic materials are also provided. Such catalystscomprise any of the compositions disclosed herein and are effective ascatalysts in an OCM reaction using an alternative oxygen source attemperatures of 900° C. or lower, 850° C. or lower, 800° C. or lower,750° C. or lower, 700° C. or lower or even 650° C. or lower. In someembodiments of the above, the catalyst is a nanowire catalyst.

Examples of OCM catalysts that use CO₂ or other oxygen sources ratherthan O₂ include, but are not limited to, catalysts comprising La₂O₃/ZnO,CeO₂/ZnO, CaO/ZnO, CaO/CeO₂, CaO/Cr₂O₃, CaO/MnO₂, SrO/ZnO, SrO/CeO₂,SrO/Cr₂O₃, SrO/MnO₂, SrCO₃/MnO₂, BaO/ZnO, BaO/CeO₂, BaO/Cr₂O₃, BaO/MnO₂,CaO/MnO/CeO₂, Na₂WO₄/Mn/SiO₂, Pr₂O₃, Tb₂O₃.

Some embodiments provide a method for performing OCM, wherein a mixtureof an OCM catalyst which use O₂ as an oxygen source (referred to hereinas an O₂-OCM catalyst) and an OCM catalyst which use CO₂ as an oxygensource (referred to herein as a CO₂-OCM catalyst) is employed as thecatalytic material, for example in a catalyst bed. Such methods havecertain advantages. For example, the CO₂-OCM reaction is endothermic andthe O₂-OCM reaction is exothermic, and thus if the right mixture and/orarrangement of CO₂-OCM and O₂-OCM catalysts is used, the methods areparticularily useful for controlling the exotherm of the OCM reaction.In some embodiments, the catalyst bed comprises a mixture of O₂-OCMcatalyst and CO₂-OCM catalysts. The mixture may be in a ratio of 1:99 to99:1. The two catalysts work synergistically as the O₂-OCM catalystsupplies the CO₂-OCM catalyst with the necessary carbon dioxide and theendothermic nature of the C₂-OCM reaction serves to control the exothermof the overall reaction. Alternatively, the CO₂ source may be externalto the reaction (e.g., fed in from a CO₂ tank, or other source) and/orthe heat required for the CO₂-OCM reaction is supplied from an externalsource (e.g., heating the reactor).

Since the gas composition will tend to become enriched in CO₂ as itflows through the catalyst bed (i.e., as the OCM reaction proceeds, moreCO₂ is produced), some embodiments of the present invention provide anOCM method wherein the catalyst bed comprises a gradient of catalystswhich changes from a high concentration of O₂-OCM catalysts at the frontof the bed to a high concentration of CO₂-OCM catalysts at the end ofthe catalyst bed.

The O₂-OCM catalyst and CO₂ OCM catalyst may have the same or differentcompositions. For example, in some embodiments the O₂-OCM catalyst andCO₂-OCM catalyst have the same composition but different morphologies(e.g., nanowire, bent nanowire, bulk, etc.). In other embodiments theO₂-OCM and the CO₂-OCM catalyst have different compositions.

Furthermore, CO₂-OCM catalysts will typically have higher selectivity,but lower yields than an O₂-OCM catalyst. Accordingly, in one embodimentthe methods comprise use of a mixture of an O₂-OCM catalyst and aCO₂-OCM catalyst and performing the reaction in O₂ deprived environmentso that the CO₂-OCM reaction is favored and the selectivity isincreased. Under appropriate conditions the yield and selectivity of theOCM reaction can thus be optimized.

In some other embodiments, the catalyst bed comprises a mixture of oneor more low temperature O₂-OCM catalyst (i.e., a catalyst active at lowtemperatures, for example less than 700° C.) and one or more hightemperature CO₂-OCM catalyst (i.e., a catalyst active at hightemperatures, for example 800° C. or higher). Here, the required hightemperature for the CO₂-OCM may be provided by the hotspots produced bythe O₂-OCM catalyst. In such a scenario, the mixture may be sufficientlycoarse such that the hotspots are not being excessively cooled down byexcessive dilution effect.

In other embodiments, the catalyst bed comprises alternating layers ofO₂-OCM and CO₂-OCM catalysts. The catalyst layer stack may begin with alayer of O₂-OCM catalyst, so that it can supply the next layer (e.g., aCO₂-OCM layer) with the necessary CO₂. The O₂-OCM layer thickness may beoptimized to be the smallest at which O₂ conversion is 100% and thus theCH₄ conversion of the layer is maximized. The catalyst bed may compriseany number of catalyst layers, for example the overall number of layersmay be optimized to maximize the overall CH₄ conversion and C2selectivity.

In some embodiments, the catalyst bed comprises alternating layers oflow temperature O₂-OCM catalysts and high temperature CO₂-OCM catalysts.Since the CO₂-OCM reaction is endothermic, the layers of CO₂-OCMcatalyst may be sufficiently thin such that in can be “warmed up” by thehotspots of the O₂-OCM layers. The endothermic nature of the CO₂-OCMreaction can be advantageous for the overall thermal management of anOCM reactor. In some embodiments, the CO₂-OCM catalyst layers act as“internal” cooling for the O₂-OCM layers, thus simplifying therequirements for the cooling, for example in a tubular reactor.Therefore, an interesting cycle takes place with the endothermicreaction providing the necessary heat for the endothermic reaction andthe endothermic reaction providing the necessary cooling for theexothermic reaction.

Accordingly, one embodiment of the present invention is a method for theoxidative coupling of methane, wherein the method comprises conversionof methane to ethane and/or ethylene in the presence of a catalyticmaterial, and wherein the catalytic material comprises a bed ofalternating layers of O₂-OCM catalysts and CO₂-OCM catalysts. In otherembodiments the bed comprises a mixture (i.e., not alternating layers)of O₂-OCM catalysts and CO₂-OCM catalysts.

In other embodiments, the OCM methods include use of a jacketed reactorwith the exothermic O₂-OCM reaction in the core and the endothermicCO₂-OCM reaction in the mantel. In other embodiments, the unused CO₂ canbe recycled and reinjected into the reactor, optionally with therecycled CH₄. Additional CO₂ can also be injected to increase theoverall methane conversion and help reduce greenhouse gases.

In other embodiments, the reactor comprises alternating stages of O₂-OCMcatalyst beds and CO₂-OCM catalyst beds. The CO₂ necessary for theCO₂-OCM stages is provided by the O₂-OCM stage upstream. Additional CO₂may also be injected. The O₂ necessary for the subsequent O₂-OCM stagesis injected downstream from the CO₂-OCM stages. The CO₂-OCM stages mayprovide the necessary cooling for the O₂-OCM stages. Alternatively,separate cooling may be provided. Likewise, if necessary the inlet gasof the CO₂-OCM stages can be additionally heated, the CO₂-OCM bed can beheated or both.

In related embodiments, the CO₂ naturally occurring in natural gas isnot removed prior to performing the OCM, alternatively CO2 is added tothe feed with the recycled methane. Instead the CO₂ containing naturalgas is used as a feedstock for CO₂-OCM, thus potentially saving aseparation step. The amount of naturally occurring CO₂ in natural gasdepends on the well and the methods can be adjusted accordinglydepending on the source of the natural gas.

The foregoing methods can be generalized as a method to control thetemperature of very exothermic reactions by coupling them with anendothermic reaction that uses the same feedstock (or byproducts of theexothermic reaction) to make the same product (or a related product).This concept can be reversed, i.e. providing heat to an endothermicreaction by coupling it with an exothermic reaction. This will alsoallow a higher per pass yield in the OCM reactor.

For purpose of simplicity, the above description relating to the use ofO₂-OCM and CO₂-OCM catalysts was described in reference to the oxidativecoupling of methane (OCM); however, the same concept is applicable toother catalytic reactions including but not limited to: oxidativedehydrogenation (ODH) of alkanes to their corresponding alkenes,selective oxidation of alkanes and alkenes and alkynes, etc. Forexample, in a related embodiment, a catalyst capable of using analternative oxygen source (e.g., CO₂, H₂O, SO₂, SO₃ or combinationsthereof) to catalyze the oxidative dehydrogenation of ethane isprovided. Such catalysts, and uses thereof are described in more detailbelow.

Furthermore, the above methods are applicable for creating novelcatalysts by blending catalysts that use different reactants for thesame catalytic reactions, for example different oxidants for anoxidation reaction and at least one oxidant is a byproduct of one of thecatalytic reactions. In addition, the methods can also be generalizedfor internal temperature control of reactors by blending catalysts thatcatalyze reactions that share the same or similar products but areexothermic and endothermic, respectively. These two concepts can also becoupled together.

2. Oxidative Dehydrogenation

Worldwide demand for alkenes, especially ethylene and propylene, ishigh. The main sources for alkenes include steam cracking,fluid-catalytic-cracking and catalytic dehydrogenation. The currentindustrial processes for producing alkenes, including ethylene andpropylene, suffer from some of the same disadvantages described abovefor the OCM reaction. Accordingly, a process for the preparation ofalkenes, which is more energy efficient and has higher yield,selectivity, and conversion than current processes is needed. Applicantshave now found that nanowires, for example the exemplary nanowiresdisclosed herein, fulfill this need and provide related advantages.

In one embodiment, the disclosed nanowires are useful as catalysts forthe oxidative dehydrogenation (ODH) of hydrocarbons (e.g. alkanes,alkenes, and alkynes). For example, in one embodiment the nanowires areuseful as catalysts in an ODH reaction for the conversion of ethane orpropane to ethylene or propylene, respectively. Reaction scheme (9)depicts the oxidative dehydrogenation of hydrocarbons:C_(x)H_(y)+½O₂→C_(x)H_(y−2)+H₂O  (9)

Representative catalysts useful for the ODH reaction include, but arenot limited to nanowires comprising Zr, V, Mo, Ba, Nd, Ce, Ti, Mg, Nb,La, Sr, Sm, Cr, W, Y or Ca or oxides or combinations thereof. Activatingpromoters (i.e. dopants) comprising P, K, Ca, Ni, Cr, Nb, Mg, Au, Zn, orMo, or combinations thereof, may also be employed.

As noted above, improvements to the yield, selectivity, and/orconversion in the ODH reaction employing bulk catalysts are needed.Accordingly, in one embodiment, the present disclosure provides ananowire which posses a catalytic activity in the ODH reaction such thatthe yield, selectivity, and/or conversion is better than when the ODHreaction is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of hydrocarbon to alkene in the ODHreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of alkane to alkenecompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion ofhydrocarbon to alkene in an ODH reaction catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of alkene in an ODH reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of alkenes compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of alkene in an ODH reaction catalyzed by thenanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the ODH reaction such that the nanowire has thesame catalytic activity, but at a lower temperature, compared a catalystprepared from bulk material having the same chemical composition as thenanowire. In some embodiments the catalytic activity of the nanowires inthe ODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 20° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 50° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in theODH reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for alkenes in an ODHreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for alkenes compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the selectivity foralkenes in an ODH reaction catalyzed by the nanowire is greater than50%, greater than 60%, greater than 70%, greater than 80%, greater than90%, or greater than 95%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO or CO₂ in an ODHreaction is less than at least 0.9 times, 0.8 times, 0.5 times, 0.2times, or 0.1 times the selectivity for CO or CO₂ compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire.

In one embodiment, the nanowires disclosed herein enable efficientconversion of hydrocarbon to alkene in the ODH reaction at temperaturesless than when the corresponding bulk material is used as a catalyst.For example, in one embodiment, the nanowires disclosed herein enableefficient conversion (i.e. high yield, conversion, and/or selectivity)of hydrocarbon to alkene at temperatures of less than 800° C., less than700° C., less than 600° C., less than 500° C., less than 400° C., orless than 300° C.

The stability of the nanowires is defined as the length of time acatalyst will maintain its catalytic performance without a significantdecrease in performance (e.g., a decrease >20%, >15%, >10%, >5%, orgreater than 1% in ODH activity or alkene selectivity, etc.). In someembodiments, the nanowires have stability under conditions required forthe ODH reaction of >1 hr, >5 hrs, >10 hrs, >20 hrs, >50 hrs, >80hrs, >90 hrs, >100 hrs, >150 hrs, >200 hrs, >250 hrs, >300 hrs, >350hrs, >400 hrs, >450 hrs, >500 hrs, >550 hrs, >600 hrs, >650 hrs, >700hrs, >750 hrs, >800 hrs, >850 hrs, >900 hrs, >950 hrs, >1,000hrs, >2,000 hrs, >3,000 hrs, >4,000 hrs, >5,000 hrs, >6,000 hrs, >7,000hrs, >8,000 hrs, >9,000 hrs, >10,000 hrs, >11,000 hrs, >12,000hrs, >13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000 hrs, >17,000hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1 yrs, >2 yrs, >3 yrs, >4yrs or >5 yrs.

As noted above, one embodiment of the present disclosure is directed toa catalyst capable of using an alternative oxygen source (e.g., CO₂,H₂O, SO₂, SO₃ or combinations thereof) to catalyze the oxidativedehydrogenation of ethane is provided. For example, the ODH reaction mayproceed according to the following reaction (10):CO₂+C_(x)H_(y)→C_(x)H_(y−2)+CO+H₂O  (10)wherein x is an integer and Y is 2x+2. Compositions useful in thisregard include Fe₂O₃, Cr₂O₃, MnO₂, Ga₂O₃, Cr/SiO₂, Cr/SO₄—SiO₂,Cr—K/SO₄—SiO₂, Na₂WO₄—Mn/SiO₂, Cr—HZSM-5, Cr/Si-MCM-41 (Cr—HZSM-5 andCr/Si-MCM-41 refer to known zeolites) and MoC/SiO₂. In some embodiments,any of the foregoing catalyst compositions may be supported on SiO₂,ZrO₂, Al₂O₃, TiO₂ or combinations thereof. In certain embodiments, thecatalyst may be a nanowire catalyst and in other embodiments thecatalyst is a bulk catalyst.

The catalysts having ODH activity with alternative oxygen sources (e.g.,CO₂, referred to herein as a CO₂-ODH catalyst) have a number ofadvantages. For example, in some embodiments a method for convertingmethane to ethylene comprises use of an O₂-OCM catalyst in the presenceof a CO₂-ODH catalyst is provided. Catalytic materials comprising atleast one O₂-OCM catalyst and at least one CO₂-ODH catalyst are alsoprovided in some embodiments. This combination of catalysts results in ahigher yield of ethylene (and/or ratio of ethylene to ethane) since theCO₂ produced by the OCM reaction is consumed and used to convert ethaneto ethylene.

In one embodiment, a method for preparation of ethylene comprisesconverting methane to ethylene in the presence of two or more catalysts,wherein at least one catalyst is an O₂-OCM catalyst and at least onecatalyst is a CO₂-ODH catalyst. Such methods have certain advantages.For example, the CO2-ODH reaction is endothermic and the O₂-OCM reactionis exothermic, and thus if the right mixture and/or arrangement ofCO₂-ODH and O₂-OCM catalysts is used, the methods are particularilyuseful for controlling the exotherm of the OCM reaction. In someembodiments, the catalyst bed comprises a mixture of O₂-OCM catalyst andCO2-ODH catalysts. The mixture may be in a ratio of 1:99 to 99:1. Thetwo catalysts work synergistically as the O₂-OCM catalyst supplies theCO₂-ODH catalyst with the necessary carbon dioxide and the endothermicnature of the C₂-OCM reaction serves to control the exotherm of theoverall reaction.

Since the gas composition will tend to become enriched in CO₂ as itflows through the catalyst bed (i.e., as the OCM reaction proceeds, moreCO₂ is produced), some embodiments of the present invention provide anOCM method wherein the catalyst bed comprises a gradient of catalystswhich changes from a high concentration of O₂-OCM catalysts at the frontof the bed to a high concentration of CO₂-ODH catalysts at the end ofthe catalyst bed.

The O₂-ODH catalyst and CO₂-ODH catalyst may have the same or differentcompositions. For example, in some embodiments the O₂-ODH catalyst andCO₂-ODH catalyst have the same composition but different morphologies(e.g., nanowire, bent nanowire, bulk, etc.). In other embodiments theO₂-ODH and the CO₂-ODH catalyst have different compositions.

In other embodiments, the catalyst bed comprises alternating layers ofO₂-OCM and CO₂-ODH catalysts. The catalyst layer stack may begin with alayer of O₂-OCM catalyst, so that it can supply the next layer (e.g., aCO2-ODH layer) with the necessary CO₂. The O₂-OCM layer thickness may beoptimized to be the smallest at which O₂ conversion is 100% and thus theCH₄ conversion of the layer is maximized. The catalyst bed may compriseany number of catalyst layers, for example the overall number of layersmay be optimized to maximize the overall CH₄ conversion and C2selectivity.

In some embodiments, the catalyst bed comprises alternating layers oflow temperature O₂-OCM catalysts and high temperature CO₂-ODH catalysts.Since the CO₂-ODH reaction is endothermic, the layers of CO₂-ODHcatalyst may be sufficiently thin such that in can be “warmed up” by thehotspots of the O₂-OCM layers. The endothermic nature of the CO₂-ODHreaction can be advantageous for the overall thermal management of anOCM reactor. In some embodiments, the CO₂-ODH catalyst layers act as“internal” cooling for the O₂-OCM layers, thus simplifying therequirements for the cooling, for example in a tubular reactor.Therefore, an interesting cycle takes place with the endothermicreaction providing the necessary heat for the endothermic reaction andthe endothermic reaction providing the necessary cooling for theexothermic reaction.

Accordingly, one embodiment of the present invention is a method for theoxidative coupling of methane, wherein the method comprises conversionof methane to ethane and/or ethylene in the presence of a catalyticmaterial, and wherein the catalytic material comprises a bed ofalternating layers of O₂-OCM catalysts and CO₂-ODH catalysts. In otherembodiments the bed comprises a mixture (i.e., not alternating layers)of O₂-OCM catalysts and CO₂-ODH catalysts. Such methods increase theethylene yield and/or ratio of ethylene to ethane compared to otherknown methods.

In other embodiments, the OCM methods include use of a jacketed reactorwith the exothermic O₂-OCM reaction in the core and the endothermicCO₂-ODH reaction in the mantel. In other embodiments, the unused CO₂ canbe recycled and reinjected into the reactor, optionally with therecycled CH₄. Additional CO₂ can also be injected to increase theoverall methane conversion and help reduce greenhouse gases.

In other embodiments, the reactor comprises alternating stages of O₂-OCMcatalyst beds and CO₂-ODH catalyst beds. The CO₂ necessary for theCO₂-ODH stages is provided by the O₂-OCM stage upstream. Additional CO₂may also be injected. The O₂ necessary for the subsequent O₂-OCM stagesis injected downstream from the CO₂-ODH stages. The CO₂-ODH stages mayprovide the necessary cooling for the O₂-OCM stages. Alternatively,separate cooling may be provided. Likewise, if necessary the inlet gasof the CO₂-ODH stages can be additionally heated, the CO₂-ODH bed can beheated or both.

In related embodiments, the CO₂ naturally occurring in natural gas isnot removed prior to performing the OCM, alternatively CO₂ is added tothe feed with the recycled methane. Instead the CO₂ containing naturalgas is used as a feedstock for CO₂-ODH, thus potentially saving aseparation step. The amount of naturally occurring CO₂ in natural gasdepends on the well and the methods can be adjusted accordinglydepending on the source of the natural gas.

3. Carbon Dioxide Reforming of Methane

Carbon dioxide reforming (CDR) of methane is an attractive process forconverting CO₂ in process streams or naturally occurring sources intothe valuable chemical product, syngas (a mixture of hydrogen and carbonmonoxide). Syngas can then be manufactured into a wide range ofhydrocarbon products through processes such as the Fischer-Tropschsynthesis (discussed below) to form liquid fuels including methanol,ethanol, diesel, and gasoline. The result is a powerful technique to notonly remove CO₂ emissions but also create a new alternative source forfuels that are not derived from petroleum crude oil. The CDR reactionwith methane is exemplified in reaction scheme (11).CO₂+CH₄→2CO+2H₂  (11)

Unfortunately, no established industrial technology for CDR exists todayin spite of its tremendous potential value. While not wishing to bebound by theory, it is thought that the primary problem with CDR is dueto side-reactions from catalyst deactivation induced by carbondeposition via the Boudouard reaction (reaction scheme (12)) and/ormethane cracking (reaction scheme (13)) resulting from the hightemperature reaction conditions. The occurrence of the coking effect isintimately related to the complex reaction mechanism, and the associatedreaction kinetics of the catalysts employed in the reaction.2CO→C+CO₂  (12)CH₄→C+2H₂  (13)

While not wishing to be bound by theory, the CDR reaction is thought toproceed through a multistep surface reaction mechanism. FIG. 9schematically depicts a CDR reaction 700, in which activation anddissociation of CH₄ occurs on the metal catalyst surface 710 to formintermediate “M-C”. At the same time, absorption and activation of CO₂takes place at the oxide support surface 720 to provide intermediate“S—CO₂”, since the carbon in a CO₂ molecule as a Lewis acid tends toreact with the Lewis base center of an oxide. The final step is thereaction between the M-C species and the activated S—CO₂ to form CO.

In one embodiment, the present disclosure provides nanowires, forexample the exemplary nanowires disclosed herein, which are useful ascatalysts for the carbon dioxide reforming of methane. For example, inone embodiment the nanowires are useful as catalysts in a CDR reactionfor the production of syn gas.

Improvements to the yield, selectivity, and/or conversion in the CDRreaction employing bulk catalysts are needed. Accordingly, in oneembodiment, the nanowires posses a catalytic activity in the CDRreaction such that the yield, selectivity, and/or conversion is betterthan when the CDR reaction is catalyzed by a corresponding bulkcatalyst. In one embodiment, the disclosure provides a nanowire having acatalytic activity such that the conversion of CO₂ to CO in the CDRreaction is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the conversion of CO₂ to CO compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the conversion of CO₂to CO in a CDR reaction catalyzed by the nanowire is greater than 10%,greater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of CO in a CDR reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of CO compared to the same reaction underthe same conditions but performed with a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire. In someembodiments the yield of CO in a CDR reaction catalyzed by the nanowireis greater than 10%, greater than 20%, greater than 30%, greater than50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in a CDR reaction such that the nanowire has the sameor better catalytic activity, but at a lower temperature, compared acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in a CDR reaction is the same or better than thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 20° C. less. In some embodiments the catalytic activity of thenanowires in a CDR reaction is the same or better than the catalyticactivity of a catalyst prepared from bulk material having the samechemical composition as the nanowire, but at a temperature of at least50° C. less. In some embodiments the catalytic activity of the nanowiresin a CDR reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in aCDR reaction is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO in a CDR reaction isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the selectivity for CO compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Inother embodiments, the selectivity for CO in a CDR reaction catalyzed bythe nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO₂ to CO in the CDR reaction at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires enable efficient conversion (i.e., highyield, conversion, and/or selectivity) of CO₂ to CO at temperatures ofless than 900° C., less than 800° C., less than 700° C., less than 600°C., or less than 500° C.

4. Fischer-Tropsch Synthesis

Fischer-Tropsch synthesis (FTS) is a valuable process for convertingsynthesis gas (i.e., CO and H₂) into valuable hydrocarbon fuels, forexample, light alkenes, gasoline, diesel fuel, etc. FTS has thepotential to reduce the current reliance on the petroleum reserve andtake advantage of the abundance of coal and natural gas reserves.Current FTS processes suffer from poor yield, selectivity, conversion,catalyst deactivation, poor thermal efficiency and other relateddisadvantages. Production of alkanes via FTS is shown in reaction scheme(14), wherein n is an integer.CO+2H₂→(1/n)(C_(n)H_(2n))+H₂O  (14)

In one embodiment, nanowires are provided which are useful as catalystsin FTS processes. For example, in one embodiment the nanowires areuseful as catalysts in a FTS process for the production of alkanes.

Improvements to the yield, selectivity, and/or conversion in FTSprocesses employing bulk catalysts are needed. Accordingly, in oneembodiment, the nanowires posses a catalytic activity in an FTS processsuch that the yield, selectivity, and/or conversion is better than whenthe FTS process is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of CO to alkane in an FTS process isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the conversion of CO to alkane compared to the samereaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the conversion of CO to alkane in an FTSprocess catalyzed by the nanowire is greater than 10%, greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in an FTS process such that the nanowire has the sameor better catalytic activity, but at a lower temperature, compared acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in an FTS process is the same or better than thecatalytic activity of a catalyst prepared from bulk material having thesame chemical composition as the nanowire, but at a temperature of atleast 20° C. less. In some embodiments the catalytic activity of thenanowires in an FTS process is the same or better than the catalyticactivity of a catalyst prepared from bulk material having the samechemical composition as the nanowire, but at a temperature of at least50° C. less. In some embodiments the catalytic activity of the nanowiresin an FTS process is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 100° C.less. In some embodiments the catalytic activity of the nanowires in anFTS process is the same or better than the catalytic activity of acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire, but at a temperature of at least 200° C.less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of alkane in a FTS process isgreater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0times, or 4.0 times the yield of alkane compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of alkane in an FTS process catalyzed by thenanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for alkanes in an FTSprocess is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for alkanes compared tothe same reaction under the same conditions but performed with acatalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In other embodiments, the selectivity foralkanes in an FTS process catalyzed by the nanowire is greater than 10%,greater than 20%, greater than 30%, greater than 50%, greater than 75%,or greater than 90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO to alkanes in a CDR process at temperatures less thanwhen the corresponding bulk material is used as a catalyst. For example,in one embodiment, the nanowires enable efficient conversion (i.e., highyield, conversion, and/or selectivity) of CO to alkanes at temperaturesof less than 400° C., less than 300° C., less than 250° C., less than200° C., less the 150° C., less than 100° C. or less than 50° C.

5. Oxidation of CO

Carbon monoxide (CO) is a toxic gas and can convert hemoglobin tocarboxyhemoglobin resulting in asphyxiation. Dangerous levels of CO canbe reduced by oxidation of CO to CO₂ as shown in reaction scheme 15:CO+½O₂→CO₂  (15)

Catalysts for the conversion of CO into CO₂ have been developed butimprovements to the known catalysts are needed. Accordingly in oneembodiment, the present disclosure provides nanowires useful ascatalysts for the oxidation of CO to CO₂.

In one embodiment, the nanowires posses a catalytic activity in aprocess for the conversion of CO into CO₂ such that the yield,selectivity, and/or conversion is better than when the oxidation of COinto CO₂ is catalyzed by a corresponding bulk catalyst. In oneembodiment, the disclosure provides a nanowire having a catalyticactivity such that the conversion of CO to CO₂ is greater than at least1.1 times, 1.25 times, 1.50 times, 2.0 times, 3.0 times, or 4.0 timesthe conversion of CO to CO₂ compared to the same reaction under the sameconditions but performed with a catalyst prepared from bulk material andhaving the same chemical composition as the nanowire. In otherembodiments, the conversion of CO to CO₂ catalyzed by the nanowire isgreater than 10%, greater than 20%, greater than 30%, greater than 50%,greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of CO₂ from the oxidation of COis greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times,3.0 times, or 4.0 times the yield of CO₂ compared to the same reactionunder the same conditions but performed with a catalyst prepared frombulk material having the same chemical composition as the nanowire. Insome embodiments the yield of CO₂ from the oxidation of CO catalyzed bythe nanowire is greater than 10%, greater than 20%, greater than 30%,greater than 50%, greater than 75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in an oxidation of CO reaction such that the nanowirehas the same or better catalytic activity, but at a lower temperature,compared a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the catalytic activityof the nanowires in an oxidation of CO reaction is the same or betterthan the catalytic activity of a catalyst prepared from bulk materialhaving the same chemical composition as the nanowire, but at atemperature of at least 20° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 50° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 100° C. less. In some embodiments the catalyticactivity of the nanowires in an oxidation of CO reaction is the same orbetter than the catalytic activity of a catalyst prepared from bulkmaterial having the same chemical composition as the nanowire, but at atemperature of at least 200° C. less.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the selectivity for CO₂ in the oxidation ofCO is greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0times, 3.0 times, or 4.0 times the selectivity for CO₂ compared to thesame reaction under the same conditions but performed with a catalystprepared from bulk material having the same chemical composition as thenanowire. In other embodiments, the selectivity for CO₂ in the oxidationof CO catalyzed by the nanowire is greater than 10%, greater than 20%,greater than 30%, greater than 50%, greater than 75%, or greater than90%.

In one embodiment, the nanowires disclosed herein enable efficientconversion of CO to CO₂ at temperatures less than when the correspondingbulk material is used as a catalyst. For example, in one embodiment, thenanowires enable efficient conversion (i.e., high yield, conversion,and/or selectivity) of CO to CO₂ at temperatures of less than 500° C.,less than 400° C., less than 300° C., less than 200° C., less than 100°C., less than 50° C. or less than 20° C.

Although various reactions have been described in detail, the disclosednanowires are useful as catalysts in a variety of other reactions. Ingeneral, the disclosed nanowires find utility in any reaction utilizinga heterogeneous catalyst and have a catalytic activity such that theyield, conversion, and/or selectivity in reaction catalyzed by thenanowires is better than the yield, conversion and/or selectivity in thesame reaction catalyzed by a corresponding bulk catalyst.

6. Combustion of Hydrocarbons

In another embodiment, the present disclosure provides a nanowire havingcatalytic activity in a reaction for the catalyzed combustion ofhydrocarbons. Such catalytic reactions find utility in catalyticconverters for automobiles, for example by removal of unburnedhydrocarbons in the exhaust by catalytic combustion or oxidation of sootcaptured on catalyzed particle filters resulting in reduction on dieselemissions from the engine. When running “cold”, the exhausts temperatureof a diesel engine is quite low, thus a low temperature catalyst, suchas the disclosed nanowires, is needed to efficiently eliminate allunburned hydrocarbons. In addition, in case of soot removal on catalyzedparticulate filters, intimate contact between the soot and the catalystis require; the open mesh morphology of nanowire catalyst coating isadvantageous to promote such intimate contact between soot and oxidationcatalyst.

In contrast to a corresponding bulk catalyst, Applicants have found thatcertain nanowires, for example the exemplary nanowires disclosed herein,posses a catalytic activity (for example because of their morphology) inthe combustion of hydrocarbons or soot such that the yield, selectivity,and/or conversion is better than when the combustion of hydrocarbons iscatalyzed by a corresponding bulk catalyst. In one embodiment, thedisclosure provides a nanowire having a catalytic activity such that thecombustion of hydrocarbons is greater than at least 1.1 times, 1.25times, 1.50 times, 2.0 times, 3.0 times, or 4.0 times the combustion ofhydrocarbons compared to the same reaction under the same conditions butperformed with a catalyst prepared from bulk material having the samechemical composition as the nanowire. In other embodiments, the totalcombustion of hydrocarbons catalyzed by the nanowire is greater than10%, greater than 20%, greater than 30%, greater than 50%, greater than75%, or greater than 90%.

In another embodiment, the disclosure provides a nanowire having acatalytic activity such that the yield of combusted hydrocarbon productsis greater than at least 1.1 times, 1.25 times, 1.50 times, 2.0 times,3.0 times, or 4.0 times the yield of combusted hydrocarbon productscompared to the same reaction under the same conditions but performedwith a catalyst prepared from bulk material having the same chemicalcomposition as the nanowire. In some embodiments the yield of combustedhydrocarbon products in a reaction catalyzed by the nanowire is greaterthan 10%, greater than 20%, greater than 30%, greater than 50%, greaterthan 75%, or greater than 90%.

The stability of the nanowires is defined as the length of time acatalyst will maintain its catalytic performance without a significantdecrease in performance (e.g., a decrease >20%, >15%, >10%, >5%, orgreater than 1% in hydrocarbon or soot combustion activity). In someembodiments, the nanowires have stability under conditions required forthe hydrocarbon combustion reaction of >1 hr, >5 hrs, >10 hrs, >20hrs, >50 hrs, >80 hrs, >90 hrs, >100 hrs, >150 hrs, >200 hrs, >250hrs, >300 hrs, >350 hrs, >400 hrs, >450 hrs, >500 hrs, >550 hrs, >600hrs, >650 hrs, >700 hrs, >750 hrs, >800 hrs, >850 hrs, >900 hrs, >950hrs, >1,000 hrs, >2,000 hrs, >3,000 hrs, >4,000 hrs, >5,000 hrs, >6,000hrs, >7,000 hrs, >8,000 hrs, >9,000 hrs, >10,000 hrs, >11,000hrs, >12,000 hrs, >13,000 hrs, >14,000 hrs, >15,000 hrs, >16,000hrs, >17,000 hrs, >18,000 hrs, >19,000 hrs, >20,000 hrs, >1 yrs, >2yrs, >3 yrs, >4 yrs or >5 yrs.

In another embodiment, the disclosure provides a nanowire having acatalytic activity in the combustion of hydrocarbons such that thenanowire has the same or better catalytic activity, but at a lowertemperature, compared a catalyst prepared from bulk material having thesame chemical composition as the nanowire. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 20° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 50° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 100° C. less. In some embodiments thecatalytic activity of the nanowires in the combustion of hydrocarbons isthe same or better than the catalytic activity of a catalyst preparedfrom bulk material having the same chemical composition as the nanowire,but at a temperature of at least 200° C. less.

7. Evaluation of Catalytic Properties

To evaluate the catalytic properties of the nanowires in a givenreaction, for example those reactions discussed above, various methodscan be employed to collect and process data including measurements ofthe kinetics and amounts of reactants consumed and the products formed.In addition to allowing for the evaluation of the catalyticperformances, the data can also aid in designing large scale reactors,experimentally validating models and optimizing the catalytic process.

One exemplary methodology for collecting and processing data is depictedin FIG. 10. Three main steps are involved. The first step (block 750)comprises the selection of a reaction and catalyst. This influences thechoice of reactor and how it is operated, including batch, flow, etc.(block 754). Thereafter, the data of the reaction are compiled andanalyzed (block 760) to provide insights to the mechanism, rates andprocess optimization of the catalytic reaction. In addition, the dataprovide useful feedbacks for further design modifications of thereaction conditions. Additional methods for evaluating catalyticperformance in the laboratory and industrial settings are described in,for example, Bartholomew, C. H. et al. Fundamentals of IndustrialCatalytic Processes, Wiley-AIChE; 2Ed (1998).

As an example, in a laboratory setting, an Altamira Benchcat 200 can beemployed using a 4 mm ID diameter quartz tube with a 0.5 mm ID capillarydownstream. Quartz tubes with 2 mm or 6 mm ID can also be used.Nanowires are tested in a number of different dilutions and amounts. Insome embodiments, the range of testing is between 10 and 300 mg. In someembodiments, the nanowires are diluted with a non-reactive diluent. Thisdiluent can be quartz (SiO₂) or other inorganic materials, which areknown to be inert in the reaction condition. The purpose of the diluentis to minimize hot spots and provide an appropriate loading into thereactor. In addition, the catalyst can be blended with lesscatalytically active components as described in more detail above.

In a typical procedure, 50 mg is the total charge of nanowire,optionally including diluent. On either side of the nanowires a smallplug of glass wool is loaded to keep the nanowires in place. Athermocouple is placed on the inlet side of the nanowire bed into theglass wool to get the temperature in the reaction zone. Anotherthermocouple can be placed on the downstream end of the nanowire bedinto the catalyst bed itself to measure the exotherms, if any.

When blending the pure nanowire with diluent, the following exemplaryprocedure may be used: x (usually 10-50) mg of the catalyst (either bulkor test nanowire catalyst) is blended with (100-x) mg of diluent.Thereafter, about 2 ml of ethanol or water is added to form a slurrymixture, which is then sonicated for about 10 minutes. The slurry isthen dried in an oven at about 100-140° C. for 2 hours to removesolvent. The resulting solid mixture is then scraped out and loaded intothe reactor between the plugs of quartz wool.

Once loaded into the reactor, the reactor is inserted into the Altamirainstrument and furnace and then a temperature and flow program isstarted. In some embodiment, the total flow is 50 to 100 sccm of gasesbut this can be varied and programmed with time. In one embodiment, thetemperatures range from 450° C. to 900° C. The reactant gases compriseair or oxygen (diluted with nitrogen or argon) and methane in the caseof the OCM reaction and gas mixtures comprising ethane and/or propanewith oxygen for oxidative dehydrogenation (ODH) reactions. Other gasmixtures can be used for other reactions.

The primary analysis of these oxidation catalysis runs is the GasChromatography (GC) analysis of the feed and effluent gases. From theseanalyses, the conversion of the oxygen and alkane feed gases can easilybe attained and estimates of yields and selectivities of the productsand by-products can be determined.

The GC method developed for these experiments employs 4 columns and 2detectors and a complex valve switching system to optimize the analysis.Specifically, a flame ionization detector (FID) is used for the analysisof the hydrocarbons only. It is a highly sensitive detector thatproduces accurate and repeatable analysis of methane, ethane, ethylene,propane, propylene and all other simple alkanes and alkenes up to fivecarbons in length and down to ppm levels.

There are two columns in series to perform this analysis, the first is astripper column (alumina) which traps polar materials (including thewater by-product and any oxygenates generated) until back-flushed laterin the cycle. The second column associated with the FID is a capillaryalumina column known as a PLOT column, which performs the actualseparation of the light hydrocarbons. The water and oxygenates are notanalyzed in this method.

For the analysis of the light non-hydrocarbon gases, a ThermalConductivity Detector (TCD) may be employed which also employees twocolumns to accomplish its analysis. The target molecules for thisanalysis are CO₂, ethylene, ethane, hydrogen, oxygen, nitrogen, methaneand CO. The two columns used here are a porous polymer column known asthe Hayes Sep N, which performs some of the separation for the CO₂,ethylene and ethane. The second column is a molecular sieve column,which uses size differentiation to perform the separation. It isresponsible for the separation of H₂, O₂, N₂, methane and CO.

There is a sophisticated and timing sensitive switching between thesetwo columns in the method. In the first 2 minutes or so, the two columnsare operating in series but at about 2 minutes, the molecular sievecolumn is by-passed and the separation of the first 3 components iscompleted. At about 5-7 minutes, the columns are then placed back inseries and the light gases come off of the sieve according to theirmolecular size.

The end result is an accurate analysis of all of the aforementionedcomponents from these fixed-bed, gas phase reactions. Analysis of otherreactions and gases not specifically described above can be performed ina similar manner.

8. Downstream Products

As noted above, in one embodiment the present disclosure is directed tonanowires useful as catalysts in reactions for the preparation of anumber of valuable hydrocarbon compounds. For example, in one embodimentthe nanowires are useful as catalysts for the preparation of ethylenefrom methane via the OCM reaction. In another embodiment, the nanowiresare useful as catalysts for the preparation of ethylene or propylene viaoxidative dehydrogenation of ethane or propane, respectively. Ethyleneand propylene are valuable compounds, which can be converted into avariety of consumer products. For example, as shown in FIG. 11, ethylenecan be converted into many various compounds including low densitypolyethylene, high density polyethylene, ethylene dichloride, ethyleneoxide, ethylbenzene, linear alcohols, vinyl acetate, alkanes, alphaolefins, various hydrocarbon-based fuels, ethanol and the like. Thesecompounds can then be further processed using methods well known to oneof ordinary skill in the art to obtain other valuable chemicals andconsumer products (e.g. the downstream products shown in FIG. 11).Propylene can be analogously converted into various compounds andconsumer goods including polypropylenes, propylene oxides, propanol, andthe like.

Accordingly, in one embodiment the invention is directed to a method forthe preparation of C2 hydrocarbons via the OCM reaction, the methodcomprises contacting a catalyst as described herein with a gascomprising methane. In some embodiments the C2 hydrocarbons are selectedfrom ethane and ethylene. In other embodiments the disclosure provides amethod of preparing any of the downstream products of ethylene noted inFIG. 11. The method comprises converting ethylene into a downstreamproduct of ethylene, wherein the ethylene has been prepared via acatalytic reaction employing a nanowire, for example any of thenanowires disclosed herein. In some embodiments, the downstream productof ethylene is low density polyethylene, high density polyethylene,ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinylacetate from ethylene, wherein the ethylene has been prepared asdescribed above. In other embodiments, the downstream product ofethylene is natural gasoline. In still other embodiments, the downstreamproduct of ethylene comprises 1-hexene, 1-octene, hexane, octane,benzene, toluene, xylene or combinations thereof.

In another embodiment, a process for the preparation of ethylene frommethane comprising contacting a mixture comprising oxygen and methane ata temperature below 900° C., below 850° C., below 800° C., below 750°C., below 700° C. or below 650° C. with a nanowire catalyst as disclosedherein is provided.

In another embodiment, the disclosure provides a method of preparing aproduct comprising low density polyethylene, high density polyethylene,ethylene dichloride, ethylene oxide, ethylbenzene, ethanol or vinylacetate, alkenes, alkanes, aromatics, alcohols, or mixtures thereof. Themethod comprises converting ethylene into low density polyethylene, highdensity polyethylene, ethylene dichloride, ethylene oxide, ethylbenzene,ethanol or vinyl acetate, wherein the ethylene has been prepared via acatalytic reaction employing a nanowires, for example any of theexemplary nanowires disclosed herein.

In more specific embodiments of any of the above methods, the ethyleneis produced via an OCM or ODH reaction or combinations thereof.

In one particular embodiment, the disclosure provides a method ofpreparing a downstream product of ethylene and/or ethane, wherein thedownstream product is a hydrocarbon fuel. For example, the downstreamproduct of ethylene may be a hydrocarbon fuel such as natural gasolineor a C₄-C₁₄ hydrocarbon, including alkanes, alkenes and aromatics. Somespecific examples include 1-butene, 1-hexene, 1-octene, hexane, octane,benzene, toluene, xylenes and the like. The method comprises convertingmethane into ethylene, ethane or combinations thereof by use of acatalytic nanowire, for example any of the catalytic nanowires disclosedherein, and further oligomerizing the ethylene and/or ethane to preparea downstream product of ethylene and/or ethane. For example, the methanemay be converted to ethylene, ethane or combinations thereof via the OCMreaction as discussed above. The catalytic nanowire may be any nanowireand is not limited with respect to morphology or composition. Thecatalytic nanowire may be an inorganic catalytic polycrystallinenanowire, the nanowire having a ratio of effective length to actuallength of less than one and an aspect ratio of greater than ten asmeasured by TEM in bright field mode at 5 keV, wherein the nanowirecomprises one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof. Alternatively, thecatalytic nanowire may be an inorganic nanowire comprising one or moremetal elements from any of Groups 1 through 7, lanthanides, actinides orcombinations thereof and a dopant comprising a metal element, asemi-metal element, a non-metal element or combinations thereof. Thenanowires may additionally comprise any number of doping elements asdiscussed above.

As depicted in FIG. 21, the method begins with charging methane (e.g.,as a component in natural gas) into an OCM reactor. The OCM reaction maythen be performed utilizing a nanowire under any variety of conditions.Water and CO₂ are optionally removed from the effluent and unreactedmethane is recirculated to the OCM reactor.

Ethylene is recovered and charged to an oligomerization reactor.Optionally the ethylene stream may contain CO₂, H₂O, N₂, ethane, C3'sand/or higher hydrocarbons. Oligomerization to higher hydrocarbons(e.g., C₄-C₁₄) then proceeds under any number of conditions known tothose of skill in the art. For example oligomerization may be effectedby use of any number of catalysts known to those skilled in the art.Examples of such catalysts include catalytic zeolites, crystallineborosilicate molecular sieves, homogeneous metal halide catalysts, Crcatalysts with pyrrole ligands or other catalysts. Exemplary methods forthe conversion of ethylene into higher hydrocarbon products aredisclosed in the following references: Catalysis Science & Technology(2011), 1(1), 69-75; Coordination Chemistry Reviews (2011), 255(7-8),861-880; Eur. Pat. Appl. (2011), EP 2287142 A1 20110223; Organometallics(2011), 30(5), 935-941; Designed Monomers and Polymers (2011), 14(1),1-23; Journal of Organometallic Chemistry 689 (2004) 3641-3668;Chemistry—A European Journal (2010), 16(26), 7670-7676; Acc. Chem. Res.2005, 38, 784-793; Journal of Organometallic Chemistry, 695 (10-11):1541-1549 May 15, 2010; Catalysis Today Volume 6, Issue 3, January 1990,Pages 329-349; U.S. Pat. Nos. 5,968,866; 6,800,702; 6,521,806;7,829,749; 7,867,938; 7,910,670; 7,414,006 and Chem. Commun., 2002,858-859, each of which are hereby incorporated in their entirety byreference.

In certain embodiments, the exemplary OCM and oligomerization modulesdepicted in FIG. 21 may be adapted to be at the site of natural gasproduction, for example a natural gas field. Thus the natural gas can beefficiently converted to more valuable and readily transportablehydrocarbon commodities without the need for transport of the naturalgas to a processing facility.

Referring to FIG. 21, “natural gasoline” refers to a mixture ofoligomerized ethylene products. In this regard, natural gasolinecomprises hydrocarbons containing 5 or more carbon atoms. Exemplarycomponents of natural gasoline include linear, branched or cyclicalkanes, alkenes and alkynes, as well as aromatic hydrocarbons. Forexample, in some embodiments the natural gasoline comprises 1-pentene,1-hexene, cyclohexene, 1-octene, benzene, toluene, dimethyl benzene,xylenes, napthalene, or other oligomerized ethylene products orcombinations thereof. In some embodiments, natural gasoline may alsoinclude C3 and C4 hydrocarbons dissolved within the liquid naturalgasoline. This mixture finds particular utility in any number ofindustrial applications, for example natural gasoline is used asfeedstock in oil refineries, as fuel blend stock by operators of fuelterminals, as diluents for heavy oils in oil pipelines and otherapplications. Other uses for natural gasoline are well-known to those ofskill in the art.

EXAMPLES Example 1 Genetic Engineering/Preparation of Phage

Phage were amplified in DH5 derivative E. coli (New England Biolabs,NEB5-alpha F′ lq; genotype: F″ proA+B+laclq Δ(lacZ)M15 zzf::Tn10(TetR)/fhuA2Δ(argF-lacZ)U169 phoA glnV44 φ80Δ(lacZ)M15 gyrA96 recA1endA1 thi-1 hsdR17) and purified using standard polyethylene glycol andsodium chloride precipitation protocols as described in the followingreferences: Kay, B. K.; Winter, J.; McCafferty, J. Phage Display ofPeptides and Proteins: A Laboratory Manual; Academic Press: San Diego(1996); C. F. Barbas, et al., ed., Phage Display: A Laboratory Manual;Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., USA(2001); and Joseph Sambrook and David W. Russell, Molecular Cloning, 3rdedition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.,USA, 2001.

Example 2 Preparation of Phage Solutions

The phage solutions were additionally purified by centrifuging at anacceleration of 10000 g at least once (until no precipitated materialwas observed), decanting the supernatant and splitting it in 50 mlcontainers, which were then stored frozen at −20° C. The frozen phagesolutions were thawed only shortly before being used.

The concentration of the phage solutions was measured using a UV-VISspectrometer. The concentration of each of the frozen phage aliquots wasmeasured prior to use. This spectroscopic method relies on theabsorption of the nucleotides in the DNA of the phage and is describedin more detail in “Phage Display: A Laboratory Manual” by Barbas,Burton, Scott and Silverman (Cold Spring Harbor Laboratory Press, 2001).The concentration of phage solutions is expressed in pfu/ml (plagueforming units per milliliter).

Example 3 Preparation Mg(OH)₂ Nanowires

FIG. 12 shows a generic reaction scheme for preparing MgO nanowires(with dopant). First, the phage solution is thawed and its concentrationdetermined according to the method described above. The phage solutionis diluted with water to adjust its concentration in the reactionmixture (i.e. with all the ingredients added) to the desired value,typically 5e12 pfu/ml or higher. The reaction container can be anythingfrom a small vial (for milliliter scale reactions) up to large bottles(for liter reaction scale reactions).

A magnesium solution and a base solution are added to the phage solutionin order to precipitate Mg(OH)₂. The magnesium solution can be of anysoluble magnesium salt, e.g. MgX2.6H₂O (X=Cl, Br, I), Mg(NO₃)₂, MgSO₄,magnesium acetate, etc. The range of the magnesium concentration in thereaction mixture is quite narrow, typically at 0.01M. The combination ofthe phage concentration and the magnesium concentration (i.e. the ratiobetween the pVIII proteins and magnesium ions) is very important indetermining both the nanowires formation process window and theirmorphology.

The base can be any alkali metal hydroxide (e.g. LiOH, NaOH, KOH),soluble alkaline earth metal hydroxide (e.g. Sr(OH)₂, Ba(OH)₂) or anyammonium hydroxide (e.g., NR₄OH, R=H, CH₃, C₂H₅, etc.). Certainselection criteria for the base include: adequate solubility (at leastseveral orders of magnitude higher than Mg(OH)₂ for Mg(OH)₂ nanowires),high enough strength (pH of the reaction mixture should be at least 11)and an inability to coordinate magnesium (for Mg(OH)₂ nanowires) to formsoluble products. LiOH is a preferred choice for Mg(OH)₂ nanowiresformation because lithium may additionally be incorporated in theMg(OH)₂ as a dopant, providing a Li/MgO doped catalyst for OCM.

Another factor concerning the base is the amount of base used or theconcentration ratio of OH⁻/Mg²⁺, i.e. the ratio between the number of OHequivalents added and the number of moles of Mg added. In order to fullyconvert the Mg ions in solution to Mg(OH)₂, the OH/Mg ratio needed is 2.The OH⁻/Mg²⁺ used in the formation of Mg(OH)₂ nanowires ranges from 0.5to 2 and, depending on this ratio, the morphology of the reactionproduct changes from thin nanowires to agglomerations of nanoparticles.The OH⁻/Mg²⁺ ratio is determined by the pH of the reaction mixture,which needs to be at least 11. If the pH is below 11, no precipitationis observed, i.e. no Mg(OH)₂ is formed. If the pH is above 12, themorphology of the nanowires begins to change and more nanoparticles areobtained, i.e. non-selective precipitation.

Considering the narrow window of magnesium concentration in whichMg(OH)₂ nanowires can be obtained, the other key synthetic parametersthat determine the nanowires formation and morphology include but arenot limited to: phage sequence and concentration thereof, theconcentration ratio of Mg²⁺/pVIII protein, the concentration ratio ofOH⁻/Mg²⁺, the incubation time of phage and Mg²⁺; incubation time ofphage and the OH⁻; the sequence of adding anion and metal ions; pH; thesolution temperature in the incubation step and/or growth step; thetypes of metal precursor salt (e.g., MgCl₂ or Mg(NO₃)₂); the types ofanion precursor (e.g., NaOH or LiOH); the number of additions; the timethat lapses between the additions of the metal salt and anion precursor,including, e.g., simultaneous (zero lapse) or sequential additions.

The Mg salt solution and the base were added sequentially, separated byan incubation time (i.e., the first incubation time). The sequence ofaddition has an effect on the morphology of the nanowires. The firstincubation time can be at least 1 h and it should be longer in the casethe magnesium salt solution is added first. The Mg salt solution and thebase can be added in a single “shot” or in a continuous slow flow usinga syringe pump or in multiple small shots using a liquid dispenserrobot. The reaction is then carried either unstirred or with only mildto moderate stirring for a specific time (i.e., the second incubationtime). The second incubation time is not as strong a factor in thesynthesis of Mg(OH)₂ nanowires, but it should be long enough for thenanowires to precipitate out of the reaction solution (e.g., severalminutes). For practical reasons, the second incubation time can be aslong as several hours. The reaction temperature can be anything fromjust above freezing temperature (e.g., 4° C.) up to 80° C. Thetemperature affects the nanowires morphology.

The precipitated Mg(OH)₂ nanowires are isolated by centrifuging thereaction mixture and decanting the supernatant. The precipitatedmaterial is then washed at least once with a water solution with pH>10to avoid redissolution of the Mg(OH)₂ nanowires. Typically, the washingsolution used can be ammonium hydroxide water solution or an alkalimetal hydroxide solution (e.g., LiOH, NaOH, KOH). This mixture iscentrifuged and the supernatant decanted. Finally, the product can beeither dried (see, Example 5) or resuspended in ethanol for TEManalysis.

The decanted supernatant of the reaction mixture can be analyzed byUV-VIS to determine the phage concentration (see, Example 2) and thusgive an estimate of the amount of phage incorporated in the precipitatedMg(OH)₂, i.e. the amount of “mineralized” phage.

FIG. 12 depicts one embodiment for preparing Mg(OH)₂ nanowires. In adifferent embodiment, the order of addition may be reversed, for examplein an exemplary 4 ml scale synthesis of Mg(OH)₂ nanowires, 3.94 ml ofconcentrated solution of phages (e.g., SEQ ID NO: 3 at a concentrationof ˜5E12 pfu/ml) were mixed in a 8 ml vial with 0.02 ml of 1 M LiOHaqueous solution and left incubating overnight (˜15 h). 0.04 ml of 1 MMgCl₂ aqueous solution were then added using a pipette and the mixturewas mixed by gentle shaking. The reaction mixture was left incubatingunstirred for 24 h. After the incubation time, the mixture wascentrifuged, and the supernatant was decanted and saved for phageconcentration measurement by UV-VIS. The precipitated material wasresuspended in 2 ml of 0.001 M LiOH aqueous solution (pH=11), themixture was centrifuged and the supernatant decanted. The obtainedMg(OH)₂ nanowires were characterized by TEM as described in Example 4.

Example 4 Characterization of Mg(OH)₂ Nanowires

Mg(OH)₂ nanowires prepared according to Example 3 were characterized byTEM in order to determine their morphology. First, a few microliters(˜500) of ethanol was used to suspend the isolated Mg(OH)₂. Thenanowires were then deposited on a TEM grid (copper grid with a verythin carbon layer) placed on filter paper to help wick out any extraliquid. After allowing the ethanol to dry, the TEM grid was loaded in aTEM and characterized. TEM was carried out at 5 KeV in bright field modein a DeLong LVEM5.

The nanowires were additionally characterized by XRD (for phaseidentification) and TGA (for calcination optimization).

Example 5 Calcination of Mg(OH)₂ Nanowires

The isolated nanowires as prepared in Example 3 were dried in an oven atrelatively low temperature (60-120° C.) prior to calcination.

The dried material was placed in a ceramic boat and calcined in air at450 C.° in order to convert the Mg(OH)₂ nanowires into MgO nanowires.The calcination recipe can be varied considerably. For example, thecalcination can be done relatively quickly like in these two examples:

-   -   load in a muffle oven preheated at 450° C., calcination time=120        min    -   load in a muffle oven (or tube furnace) at room temperature and        ramp to 450° C. with 5° C./min rate, calcination time=60 min

Alternatively, the calcination can be done in steps that are chosenaccording to the TGA signals like in the following example:

-   -   load in a muffle oven (or tube furnace) at room temperature,        ramp to 100° C. with 2° C./min rate, dwell for 60 min, ramp to        280° C. with 2° C./min rate, dwell for 60 min, ramp to 350° C.        with 2° C./min rate, dwell for 60 min and finally ramp to        450° C. with 2° C./min rate, dwell for 60 min.

Generally, a step recipe is preferable since it should allow for abetter, smoother and more complete conversion of Mg(OH)₂ into MgO.Optionally, the calcined product is ground into a fine powder.

FIG. 13 shows the X-ray diffraction patterns of the Mg(OH₂) nanowiresand the MgO nanowires following calcinations. Crystalline structures ofboth types of nanowires were confirmed.

Example 6 Preparation of Li Doped MgO Nanowires

Doping of nanowires is achieved by using the incipient wetnessimpregnation method. Before impregnating the MgO nanowires with thedoping solution, the maximum wettability (i.e. the ability of thenanowires to absorb the doping solution before becoming a suspension orbefore “free” liquid is observed) of the nanowires was determined. Thisis a very important step for an accurate absorption of the doping metalon the MgO surface. If too much dopant solution is added and asuspension is formed, a significant amount of dopant will crystallizeunabsorbed upon drying and if not enough dopant solution is added,significant portions of the MgO surface will not be doped.

In order to determine the maximum wettability of the MgO nanowires,small portions of water were dropped on the calcined MgO powder until asuspension was formed, i.e. until “free” liquid is observed. The maximumwettability was determined to be the total amount of water added beforethe suspension formed. The concentration of the doping solution was thencalculated so that the desired amount of dopant was contained in thevolume of doping solution corresponding to the maximum wettability ofthe MgO nanowires. In another way to describe the incipient wetnessimpregnation method, the volume of the doping solution is set to beequal to the pore volume of the nanowires, which can be determined byBET (Brunauer, Emmett, Teller) measurements. The doping solution is thendrawn into the pores by capillary action.

In one embodiment, the doping metal for MgO based catalysts for OCM islithium (see, also, FIG. 12). Thus, in one embodiment the dopant sourcecan be any soluble lithium salt as long as it does not introduceundesired contaminants. Typically, the lithium salts used were LiNO₃,LiOH or Li₂CO₃. LiNO₃ and LiOH are preferred because of their highersolubility. In one embodiment, the lithium content in MgO catalysts forOCM ranges from 0 to 10 wt % (i.e. about 0 to 56 at %).

The calculated amount of dopant solution of the desired concentrationwas dropped onto the calcined MgO nanowires. The obtained wet powder wasdried in an oven at relatively low temperature (60-120° C.) and calcinedusing one of the recipes described above. It is noted that, during thisstep, no phase transition occurs (MgO has already been formed in theprevious calcination step) and thus a step recipe (see previousparagraph) may not be necessary.

The dopant impregnation step can also be done prior to the calcination,after drying the Mg(OH)₂ nanowires isolated from the reaction mixture.In this case, the catalyst can be calcined immediately after the dopantimpregnation, i.e. no drying and second calcination steps would berequired since its goals are accomplished during the calcination step.

Three identical syntheses were made in parallel. In each synthesis, 80ml of concentrated solution of phages (SEQ ID NO: 3 at a concentrationof ≧5E12 pfu/ml) were mixed in a 100 ml glass bottle with 0.4 ml of 1 MLiOH aqueous solution and left incubating for 1 h. 0.8 ml of 1 M MgCl₂aqueous solution were added using a pipette and the mixture was mixed bygently shaking it. The reaction mixture was left incubating unstirredfor 72 h at 60° C. in an oven. After the incubation time, the mixturewas centrifuged. The precipitated material was resuspended in 20 ml of0.06 M NH₄OH aqueous solution (pH=11), the mixture was centrifuged andthe supernatant decanted. The obtained Mg(OH)₂ nanowires wereresuspended in ethanol. The ethanol suspensions of the three identicalsyntheses were combined and a few microliters of the ethanol suspensionwere used for TEM analysis. The ethanol suspension was centrifuged andthe supernatant decanted. The gel-like product was transferred in aceramic boat and dried for 1 h at 120° C. in a vacuum oven.

The dried product was calcined in a tube furnace using a step recipe(load in the furnace at room temperature, ramp to 100° C. with 2° C./minrate, dwell for 60 min, ramp to 280° C. with 2° C./min rate, dwell for60 min, ramp to 350° C. with 2° C./min rate, dwell for 60 min, ramp to450° C. with 2° C./min rate, dwell for 60 min and finally cool to roomtemperature). The yield was 24 mg. The calcined product was ground to afine powder.

10 mg of the calcined product were impregnated with a LiOH aqueoussolution. First, the maximum wettability was determined by adding waterto the calcined product in a ceramic boat until the powder was saturatedbut no “free” liquid was observed. The maximum wettability was 12 μl.Since the target doping level was 1 wt % lithium, the necessaryconcentration of the LiOH aqueous solution was calculated to be 1.2 M.The calcined product was dried again for 1 h at 120° C. to remove thewater used to determine the wettability of the powder. 12 μl of the 1.2M LiOH solution were dropped on the MgO nanowires powder. The wet powderwas dried for 1 h at 120° C. in a vacuum oven and finally calcined in amuffle oven (load at room temperature, ramp to 460° C. with 2° C./minramp, dwell for 120 min).

Example 7 Creating Diversity by Varying the Reaction Parameters

Certain synthetic parameters strongly influence the nanowire formationon phage, including selective binding of metal and/or anions, as well assurface morphologies. FIG. 14 shows a number of MgO nanowiressynthesized in the presence of different phage sequence (e.g., differentpVIII) while keeping the other reaction conditions constant. Phages ofSEQ ID NOs. 1, 7, 10, 11, 13 and 14 were the respective phage of choicein six reactions carried out in otherwise identical conditions. Theconstant reaction conditions may include: concentration ratios of Mg²⁺and active functional groups on the phage; concentration ratios ofOH⁻/Mg²⁺; incubation time of phage and Mg²⁺; incubation time of phageand OH⁻; concentration of phage; sequence of adding anion and metalions; solution temperature in the incubation step and/or growth step;etc. As shown, the morphologies of MgO nanowires are significantlyinfluenced by the phage sequences.

Thus, varying these and other reaction conditions may produce a diverseclass of nanowire catalysts. In addition, certain correlation betweenthe reaction conditions and the surface morphologies of the nanowirescan be empirically established, thus enabling rational designs ofcatalytic nanowires.

Example 8 Preparation of Sr-Doped La₂O₃ Nanowires

23 ml of 2.5 e12 pfu solution of phages (SEQ ID NO: 3) was mixed in a 40ml glass bottle with 0.046 ml of 0.1 M LaCl₃ aqueous solution and leftincubating for 16 h. After this incubation period, a slow multistepaddition is conducted with 1.15 ml of 0.05 M LaCl₃ solution and 1.84 mlof 0.3 M NH₄OH. This addition is conducted in six hours and twentysteps. The reaction mixture was left stirred another 2 h at roomtemperature. After that time the suspension was centrifuged in order toseparate the solid phase from the liquid phase. The precipitatedmaterial was then resuspended in 5 ml of water and centrifuged in orderto further remove un-reacted species. A final wash was conducted with 2ml ethanol. The gel-like product remaining is then dried for 30 minutesat 110° C. in a vacuum oven.

The dried product was then calcined in a muffle furnace using a steprecipe (load in the furnace at room temperature, ramp to 200° C. with 3°C./min rate, dwell for 120 min, ramp to 400° C. with 3° C./min rate,dwell for 120 min, cool to room temperature). The calcined product wasthen ground to a fine powder.

5 mg of the calcined product were impregnated with 0.015 ml Sr(NO₃)₂0.1M aqueous solution. Powder and solution is mixed on hot plate at 90 Cuntil forming a paste. The paste was then dried for 1 h at 120° C. in avacuum oven and finally calcined in a muffle oven in air (load in thefurnace at room temperature, ramp to 200° C. with 3° C./min rate, dwellfor 120 min, ramp to 400° C. with 3° C./min rate, dwell for 120 min,ramp to 500° C. with 3° C./min rate, dwell for 120 min, cool to roomtemperature).

Example 9 Preparation of ZrO₂/La₂O₃ Core/Shell Nanowires

As an example, FIG. 15 shows schematically an integrated process 800 forgrowing a core/shell structure of ZrO₂/La₂O₃ nanowire. A phase solutionis prepared, to which a zirconium salt precursor (e.g., ZrCl₂) is addedto allow for the nucleation of ZrO²⁺ on the phage. Subsequently, ahydroxide precursor (e.g., LiOH) is added to cause the nucleation ofhydroxide ions on the phage. Nanowires 804 is thus formed in which thephage 810 is coated with a continuous and crystalline layer 820 ofZrO(OH)₂. To this reaction mixture, a lanthanum salt precursor (e.g.,LaCl₃) is added under a condition to cause the nucleation of La(OH)₃over the ZrO(OH)₂ nanowire 804. Following calcinations, nanowires of acore/shell structure of ZrO₂/La₂O₃ are formed. A further step ofimpregnation produces nanowires of ZrO₂/La₂O₃ doped with strontium ions(Sr²⁺) 840, in which the phage 810 is coated with a layer of ZrO₂ 830,which is in turn coated with a shell of La₂O₃ 850.

ZrO₂/La₂O₃ nanowires were thus prepared by mixing 20 ml of 2.5e12 pfu E3Phage solution to 0.1 ml of 0.5M ZrO(NO₃)₂ aqueous solution. Thesolution was incubated under stirring for 16 hours. Any solids formedfollowing incubation were removed by centrifugation at 4000 rpm for 5minutes and redispersed in 0.5 ml ethanol. A small aliquot was retrievedfor TEM characterization.

Thereafter, the ethanol solution was mixed with 10 ml water and 2 ml of0.05M ZrO(NO₃)₂ with 2 ml of 0.1M NH₄OH were added during a period of200 minutes using syringe pumps. Wash solids with water and resuspend inethanol for TEM observation.

To about 18 mg of ZrO(OH)₂ nanowires in suspension, 10 ml of water wasadded, followed by the addition of 0.5 ml of LaCl₃ 0.083 M with 0.5 mlof NH₄OH 0.3 M solution during a period of 50 minutes using syringepumps. The solids thus formed were separated by centrifugation to obtaina powder, which was dried in a vacuum oven at 110° C. for one hour. Asmall aliquot of the dried powder is then suspended in ethanol for TEMobservation.

Example 10 Preparation of La(OH)₃/ZrO₂ Core/Shell Nanowires

Similar to Example 9, La(OH)₃ nanowires were coated with ZrO₂ shellaccording to the following process. To 6.8 mg of La(OH)₃ nanowires(prepared by LaCl₃ and NH₄OH in a process similar to that of Example 9),which had been dried at 110° C., was added 4 ml of water to suspend thesolids. 0.5 ml of 0.05M ZrO(NO₃)₂ and 0.5 ml of 0.1 M NH₄OH were slowlyadded in 50 minutes. The solids were retrieved by centrifugation andcalcined at 500° C. for one hour. TEM observation showed nanowires asthe major morphology.

Example 11 Preparation of Hollow-Cored ZrO₂ Nanowires

To the La(OH)₃/ZrO₂ core/shell nanowires prepared Example 10, additionalprocessing can be used to create hollow ZrO₂ shell nanowires. TheLa(OH)₃ core can be etched using 1M citric acid solution. Controlledexperiments on calcined and un-calcined La(OH)₃ nanowires shows that theentire nanowires are fully etched in about one hour at room temperature.Etching of La(OH)₃/ZrO₂ core/shell nanowires was conducted overnight(about 16 hours).

The remaining solid was then separated by centrifugation and TEMobservation is conducted on the washed solids (water wash). Low contrastzirconia nanowires were observed after etching, which indicates thathollow zirconia “straws” can be formed using La(OH)₃ nanowire astemplate.

Example 12 OCM Catalyzed by La₂O₃ Nanowires

A 20 mg sample of a phage-based Sr (5%) doped La₂O₃ catalyst was dilutedwith 80 mg of quartz sand and placed into a reactor (run WPS21). The gasflows were held constant at 9 sccm methane, 3 sccm oxygen and 6 sccm ofargon. The upstream temperature (just above the bed) was varied from500° C. to 800° C. in 100° C. increments and then decreased back down to600° C. in 50° C. increments. The vent gas analysis was gathered at eachtemperature level.

As a point of comparison, 20 mg of bulk 5% Sr on La₂O₃ catalyst wasdiluted in the same manner and run through the exact flow andtemperature protocol.

FIG. 16 shows the formation of OCM products at 700° C., including C2(ethane and ethylene) as well as further coupling products (propane andpropylene).

FIGS. 17A, 17B and 17C show the comparative results in catalyticperformance parameters for a nanowire catalyst (Sr²⁺/La₂O₃) vs. itscorresponding bulk material (Sr²⁺/La₂O₃ bulk). Methane conversion rates,C2 selectivities and C2 yields are among the important parameters bywhich the catalytic properties were measured. More specifically, FIG.17A shows the methane conversion rates are higher for the nanowirecatalyst compared to the bulk material across a wide temperature range(e.g., 550 to 650° C.). Likewise, FIG. 17B and FIG. 17C show that the C2selectivities and C2 yields are also higher for the nanowire catalyst ascompared to the bulk catalyst across a wide temperature range (e.g., 550to 650° C.). Thus, it is demonstrated that by improving both conversionand selectivity simultaneously that the C2 yield can be improved overtraditional bulk catalysts.

FIGS. 18A-18B demonstrate that nanowires prepared under differentsynthetic conditions afforded different catalytic performances,suggesting that the various synthetic parameters resulted in divergentnanowire morphologies. FIG. 18A shows that nanowires prepared usingdifferent phage templates (SEQ ID NO: 9 and SEQ ID NO:3) in otherwiseidentical synthetic conditions created nanowire catalysts that performdifferently in terms of the C2 selectivity in an OCM reaction. FIG. 18Bshows the comparative C2 selectivities of nanowires prepared by analternative adjustment of the synthetic parameters. In this case, thephage template was the same for both nanowires (SEQ ID NO:3), but thesynthetic conditions were different. Specifically, the nanowires of FIG.18A were prepared with shorter incubation and growth times than thenanowires of FIG. 18B. Additionally, the nanowires of FIG. 18A werecalcined in a single step at 400° C. instead of the ramped temperaturecalcinations performed on the nanowires of FIG. 18B.

These results confirm that the nanowire catalysts behave differentlyfrom their bulk material counterparts. In particular, the nanowirecatalysts allow for adjustments of the surface morphologies throughsynthetic design and screening to ultimately produce high-performancecatalysts.

Example 13 Oxidative Dehydrogenation Catalyzed by MgO Nanowires

A 10 mg sample of phage-based Li doped MgO catalyst was diluted with 90mg of quartz sand and placed in a reactor. The gas flows were heldconstant at 8 sccm alkane mix, 2 sccm oxygen and 10 sccm of argon. Theupstream temperature (just above the bed) was varied from 500° C. to750° C. in 50-100° C. increments. The vent gas analysis was gathered ateach temperature level.

As a point of comparison, 10 mg of bulk 1 wt % Li on MgO catalyst wasdiluted in the same manner and run through the exact flow andtemperature protocol. The results of this experiment are shown in FIG.19. As can be seen in FIG. 19, phage-based nanowires according to thepresent disclosure comprise better conversion of ethane and propanecompared to a corresponding bulk catalyst.

Example 14 Synthesis of Sr Doped La₂O₃ Nanowires

Sr doped La₂O₃ nanowires were prepared according to the followingnon-template directed method.

A La(OH)₃ gel was prepared by adding 0.395 g of NH₄OH (25%) to 19.2 mlof water followed by addition of 2 ml of a 1 M solution of La(NO₃)₃. Thesolution was then mixed vigorously. The solution first gelled but theviscosity dropped with continuous agitation. The solution was thenallowed to stand for a period of between 5 and 10 minutes. The solutionwas then centrifuged at 10,000 g for 5 minutes. The centrifuged gel wasretrieved and washed with 30 ml of water and the centrifugation washingprocedure was repeated.

To the washed gel was added 10.8 ml of water to suspend the solid. Thesuspension was then transferred to a hydrothermal bomb (20 ml volume,not stirred). The hydrothermal bomb was then loaded in a muffle furnaceat 160° C. and the solution was allowed to stand under autogenouspressure at 160° C. for 16 hours.

The solids were then isolated by centrifugation at 10,000 g for 5minutes, and wash with 10 ml of water to yield about 260 mg of solid(after drying for 1 h at 120° C. in a vacuum oven).

A 57 mg aliquot of nanowires was then mixed with 0.174 ml of a 0.1 Msolution of Sr(NO₃)₂. This mixture was then stirred on a hot plate at90° C. until a paste was formed.

The paste was then dried for 1 h at 120° C. in a vacuum oven and finallycalcined in a muffle oven in air according to the following procedure:(1) load in the furnace at room temperature; (2) ramp to 200° C. with 3°C./min rate; (3) dwell for 120 min; (3) ramp to 400° C. with 3° C./minrate; (4) dwell for 120 min; (5) ramp to 500° C. with 3° C./min rate;and (6) dwell for 120 min. The calcined product was then ground to afine powder.

FIG. 20 shows a TEM image of the nanowires obtained from thisnon-template directed method. As shown in FIG. 20, the nanowirescomprise a ratio of effective length to actual length of about 1 (i.e.,the nanowires comprise a “straight” morphology).

Example 15 Synthesis of La₂O₃ Nanowires

La(NO₃)₃.6 H₂O (10.825 g) is added to 250 mL distilled water and stirreduntil all solids are dissolved. Concentrated ammonium hydroxide (4.885mL) is added to this mixture and stirred for at least one hour resultingin a white gel. This mixture is transferred equally to 5 centrifugetubes and centrifuged for at least 15 minutes. The supernatant isdiscarded and each pellet is rinsed with water, centrifuged for at least15 minutes and the supernatant is again discarded.

The resulting pellets are all combined, suspended in distilled water(125 mL) and heated at 105° C. for 24 hours. The lanthanum hydroxide isisolated by centrifugation and suspended in ethanol (20 mL). The ethanolsupernatant is concentrated and the product is dried at 65° C. until allethanol is removed.

The lanthanum hydroxide nanowires prepared above are calcined by heatingat 100° C. for 30 min., 400° C. for 4 hours and then 550° C. for 4 hoursto obtain the La₂O₃ nanowires.

Example 16 Preparation of Na₁₀MnW₅O₁₇ Nanowires

25 ml of concentrated reagent grade NH₄OH are dissolved in 25 ml ofdistilled water, and 1 ml of 0.001M aqueous solution of M13bacteriophage is then added. 0.62 g of Mn(NO₃)₂, 1.01 g of NaCl and 2.00g of WO₃ are then added to the mixture with stirring. The mixture isheated at a temperature of about 95° C. for 15 minutes. The mixture isthen dried overnight at about 110° C. and calcined at about 400° C. for3 hours.

Example 17 Preparation of Na₁₀MnW₅O₁₇ Nanowires

25 ml of concentrated reagent grade NH₄OH are dissolved in 25 ml ofdistilled water, and 1 ml of 0.001 M aqueous solution of M13bacteriophage is then added. 1.01 g of NaCl and 2.00 g of WO₃ are thenadded to the mixture with stirring. The mixture is heated at atemperature of about 95° C. for 15 minutes. The mixture is then driedovernight at about 110° C. and calcined at about 400° C. for 3 hours.The resulting material is then suspended in 10 ml of distilled water and0.62 g of Mn(NO₃)₂ is added to the mixture with stirring. The mixture isheated at a temperature of about 115° C. for 15 minutes. The mixture isthen dried overnight at about 110° C. and calcined at about 400° C. for3 hours.

Example 18 Preparation of Na₁₀MnW₅O₁₇/SiO₂ Nanowires

Nanowire material Na₁₀MnW₅O₁₇ (2.00 g), prepared as described in Example16 above, is suspended in water, and about 221.20 g of a 40% by weightcolloidal dispersion of SiO₂ (silica) is added while stirring. Themixture is heated at about 100° C. until near dryness. The mixture isthen dried overnight at about 110° C. and heated under a stream ofoxygen gas (i.e., calcined) at about 400° C. for 3 hours. The calcinedproduct is cooled to room temperature and then ground to a 10-30 meshsize.

Example 19 Preparation of La₂O₃ Nanowires

Two identical syntheses were made in parallel. In each synthesis, 360 mlof 4 e12 pfu/ml solution of phage (SEQ ID NO: 3) were mixed in a 500 mlplastic bottle with 1.6 ml of 0.1 M LaCl3 aqueous solution and leftincubating for at least 1 hour. After this incubation period, a slowmultistep addition was conducted with 20 ml of 0.1 M LaCl3 solution and40 ml of 0.3 M NH4OH. This addition was conducted in 24 hours and 100steps. The reaction mixture was left stirred for at least another hourat room temperature. After that time the suspension was centrifuged inorder to separate the solid phase from the liquid phase. Theprecipitated material was then re-suspended in 25 ml of ethanol. Theethanol suspensions from the two identical syntheses were combined andcentrifuged in order to remove un-reacted species. The gel-like productremaining was then dried for 15 hours at 65° C. in an oven and thencalcined in a muffle oven in air (load in the furnace at roomtemperature, ramp to 100° C. with 2° C./min rate, dwell for 30 min, rampto 400° C. with 2° C./min rate, dwell for 240 min, ramp to 550° C. with2° C./min rate, dwell for 240 min, cool to room temperature).

Example 20 Preparation of Mg/Na Doped La₂O₃ Nanowires

Two identical syntheses were made in parallel. In each synthesis, 360 mlof 4 e12 pfu solution of phage (SEQ ID NO: 3) were mixed in a 500 mlplastic bottle with 1.6 ml of 0.1 M LaCl₃ aqueous solution and leftincubating for at least 1 hour. After this incubation period, a slowmultistep addition was conducted with 20 ml of 0.1 M LaCl₃ solution and40 ml of 0.3 M NH₄OH. This addition was conducted in 24 hours and 100steps. The reaction mixture was left stirred for at least another hourat room temperature. After that time, the suspension was centrifuged inorder to separate the solid phase from the liquid phase. Theprecipitated material was then resuspended in 25 ml of ethanol. Theethanol suspensions from the two identical syntheses were combined andcentrifuged in order to remove un-reacted species. The gel-like productremaining was then dried for 15 hours at 65° C. in an oven.

The target doping level was 20 at % Mg and 5 at % Na at % refers toatomic percent). 182 mg of the dried product were suspended in 2.16 mldeionized water, 0.19 ml 1 M Mg(NO₃)₂ aqueous solution and 0.05 ml 1MNaNO₃ aqueous solution. The resulting slurry was stirred at roomtemperature for 1 hour, sonicated for 5 min, then dried at 120° C. inand oven until the powder was fully dried and finally calcined in amuffle oven in air (load in the furnace at room temperature, ramp to100° C. with 2° C./min rate, dwell for 30 min, ramp to 400° C. with 2°C./min rate, dwell for 60 min, ramp to 550° C. with 2° C./min rate,dwell for 60 min, ramp to 650° C. with 2° C./min rate, dwell for 60 min,ramp to 750° C. with 2° C./min rate, dwell for 240 min, cool to roomtemperature).

Example 21 Oxidative Coupling of Methane Catalyzed by Mg/Na Doped La₂O₃Nanowires

50 mg of Mg/Na-doped La₂O₃ nanowires catalyst from example 20 wereplaced into a reactor tube (4 mm ID diameter quartz tube with a 0.5 mmID capillary downstream), which was then tested in an Altamira Benchcat203. The gas flows were held constant at 46 sccm methane and 54 sccmair, which correspond to a CH₄/O₂ ratio of 4 and a feed gas-hour spacevelocity (GHSV) of about 130000/hour. The reactor temperature was variedfrom 400° C. to 450° C. in a 50° C. increment, from 450° C. to 550° C.in 25° C. increments and from 550° C. to 750° C. in 50° C. increments.The vent gases were analyzed with gas chromatography (GC) at eachtemperature level.

FIG. 22 shows the onset of OCM between 550° C. and 600° C. The C2selectivity, methane conversion and C2 yield at 650° C. were 57%, 25%and 14%, respectively.

In another example, 50 mg of Mg/Na-doped La₂O₃ nanowires catalyst fromexample 20 were placed into a reactor tube (4 mm ID diameter quartz tubewith a 0.5 mm ID capillary downstream), which was then tested in anAltamira Benchcat 203. The gas flows were held constant at 46 sccmmethane and 54 sccm air, which correspond to a feed gas-hour spacevelocity (GHSV) of about 130000 h⁻¹. The CH4/O2 ratio was 5.5. Thereactor temperature was varied from 400° C. to 450° C. in a 50° C.increment, from 450° C. to 550° C. in a 25° C. increments and from 550°C. to 750° C. in 50° C. increments. The vent gases were analyzed withgas chromatography (GC) at each temperature level.

FIG. 23 shows the onset of OCM between 550° C. and 600° C. The C2selectivity, methane conversion and C2 yield at 650° C. were 62%, 20%and 12%, respectively.

Example 22 Nanowire Synthesis

Nanowires may be prepared by hydrothermal synthesis from metal hydroxidegels (made from metal salt+base). In some embodiments, this method isapplicable to lanthanides, for example La, Nd, Pr, Sm, Eu, andlanthanide containing mixed oxides.

Alternatively, nanowires can be prepared by synthesis from metalhydroxide gel (made from metal salt+base) under reflux conditions. Insome embodiments, this method is applicable to lanthanides, for exampleLa, Nd, Pr, Sm, Eu, and lanthanide containing mixed oxides.

Alternatively, the gel can be aged at room temperature. Certainembodiments of this method are applicable for making magnesiumhydroxychloride nanowires, which can be converted to magnesium hydroxidenanowires and eventually to MgO nanowires. In a related method,hydrothermal treatment of the gel instead of aging is used.

Nanowires may also be prepared by polyethyleneglycol assistedhydrothermal synthesis. For example, Mn containing nanowires may beprepared according to this method using methods known to those skilledin the art. Alternatively, hydrothermal synthesis directly from theoxide can be used.

Example 23 Preparation of Nanowires

Nanostructured catalyst materials can be prepared by a variety ofstarting materials. In certain embodiments, the rare earth oxides areattractive starting materials since they can be obtained at high purityand are less expensive than the rare earth salt precursors that aretypically used in preparative synthesis work. Methods for making rareearth oxide nanowires and derivatives thereof are described below.

Method A: Lanthanide oxide starting material can be hydrothermallytreated in the presence of ammonium halide to prepare rare earth oxidenanowires. The preparation is a simple one-pot procedure with highyield. For example, one gram of lanthanum oxide was placed in 10 mL ofdistilled water. Ammonium chloride (0.98 g) was added to the water, themixture was placed in an autoclave, and the autoclave was placed in a160 C oven for 18 h. The autoclave was taken out of the oven, cooled,and the product was isolated by filtration. Micron and submicronnanowires were observed in the TEM images of the product. This methodcould also be used to prepare mixed metal oxides, metal oxyhalides,metal oxynitrates, and metal sulfates.

Method B: Metal oxide nanowires can be prepared using a solid-statereaction of rare earth oxide or bismuth oxide in the presence ofammonium halide. The solid-state reaction is used to prepare the rareearth or bismuth oxyhalide. The metal oxyhalide is then placed in waterat room temperature and the oxyhalide is slowly converted to metal oxidewith nanowire/needle morphology. This method could also be used toprepare mixed metal oxides. For example: lanthanum oxide, bismuth oxide,and ammonium chloride were ground and fired in a ceramic dish to makethe mixed lanthanum bismuth oxychloride. The metal oxychloride is thenplaced in water to form the mixed lanthanum bismuth oxide nanowires.

Example 24 Preparation of MgO/Mn₂O₃ Core/Shell Nanowires

19.7 ml of concentrated solution of phages (e.g., SEQ ID NO: 3 at aconcentration of ˜5E12 pfu/ml) were mixed in a 20 ml vial with 0.1 ml of1 M LiOH aqueous solution and left incubating overnight (˜15 h). 0.2 mlof 1 M MgCl₂ aqueous solution were then added using a pipette, and themixture was mixed by gentle shaking. The reaction mixture was leftincubating unstirred for 72 h. After the incubation time, the mixturewas centrifuged and the supernatant decanted. The precipitated materialwas re-suspended in 5 ml of 0.001 M LiOH aqueous solution (pH=11), themixture was centrifuged and the supernatant decanted.

19.8 ml of deionized water were added to the obtained Mg(OH)₂ nanowires.The mixture was left incubating for 1 h. After the incubation time, 0.2ml of 1 M MnCl₂ aqueous solution were then added using a pipette and themixture was mixed by gentle shaking. The reaction mixture was leftincubating unstirred for 24 h. After the incubation time, the mixturewas centrifuged and the supernatant decanted. The precipitated materialwas re-suspended in 3 ml of 0.001 M LiOH aqueous solution (pH=11), themixture was centrifuged and the supernatant decanted. The precipitatedmaterial was finally re-suspended in 7 ml ethanol, the mixture wascentrifuged and the supernatant decanted.

The obtained MnO(OH) coated Mg(OH)₂ nanowires were dried at 65° C. for15 h in an oven. Finally, the dried product was calcined in a mufflefurnace using a step recipe (load in the furnace at room temperature,ramp to 100° C. with 2° C./min rate, dwell for 60 min, ramp to 280° C.with 2° C./min rate, dwell for 60 min, ramp to 350° C. with 2° C./minrate, dwell for 60 min, ramp to 450° C. with 2° C./min rate, dwell for60 min, ramp to 550° C. with 2° C./min rate, dwell for 60 min, cool toroom temperature) to convert it to MgO/Mn₂O₃ core-shell nanowires.

The surface area of the nanowires was determined by BET (Brunauer,Emmett, Teller) measurement at 111.5 m²/g.

Example 25 Preparation of Mn₂O₃ Nanowires

3.96 ml of concentrated solution of phages (e.g., SEQ ID NO: 3 at aconcentration of ˜5E12 pfu/ml) were mixed in a 8 ml vial with 0.04 ml of1 M MnCl₂ aqueous solution and left incubating for 20 h. 0.02 ml of 1 MLiOH aqueous solution were then added using a pipette and the mixturewas mixed by gentle shaking. The reaction mixture was left incubatingunstirred for 72 h. After the incubation time, the mixture wascentrifuged, and the supernatant was decanted. The precipitated materialwas re-suspended in 2 ml of 0.001 M LiOH aqueous solution (pH=11), themixture was centrifuged and the supernatant decanted. The precipitatedmaterial was re-suspended in 2 ml ethanol, the mixture was centrifugedand the supernatant decanted. The obtained MnO(OH) nanowires were driedat 65° C. for 15 h in an oven. Finally, the dried product was calcinedin a muffle furnace using a step recipe (load in the furnace at roomtemperature, ramp to 100° C. with 2° C./min rate, dwell for 60 min, rampto 280° C. with 2° C./min rate, dwell for 60 min, ramp to 350° C. with2° C./min rate, dwell for 60 min, ramp to 450° C. with 2° C./min rate,dwell for 60 min, ramp to 550° C. with 2° C./min rate, dwell for 60 min,cool to room temperature) to convert it to Mn₂O₃ nanowires.

Example 26 Preparation of V₂O₅ Nanowires

1.8 mg of V₂O₅ were dissolved in a 10 ml of a 2.5 wt % aqueous solutionof HF. 1 ml of the V₂O₅/HF solution was mixed with 1 ml of concentratedsolution of phages (e.g., SEQ ID NO: 3 at a concentration of ˜5E12pfu/ml) in a 15 ml plastic centrifugation tube and left incubating for 2h. 1 ml of a saturated solution of boric acid (supernatant of nominally1 M boric acid aqueous solution) were then added using a pipette and themixture was mixed by gentle shaking. The reaction mixture was leftincubating unstirred for 170 h. After the incubation time, the mixturewas centrifuged, and the supernatant was decanted. The precipitatedmaterial was suspended in 2 ml ethanol, the mixture was centrifuged andthe supernatant decanted. The obtained V₂O₅ nanowires were characterizedby TEM.

Example 27 Synthesis of MgO Nanowires

12.5 ml of a 4M MgCl₂ aqueous solution were heated to 70° C. on ahotplate. 0.1 g of MgO (from Aldrich) were then slowly added, over aspan of at least 5 minutes, to the solution while it was vigorouslystirred. The mixture was kept stirring at 70° C. for 3 h and then cooleddown overnight (˜15 h) without stirring.

The obtained gel was transferred in a 25 ml hydrothermal bomb (Parr BombNo. 4749). The hydrothermal bomb was then loaded in an oven at 120° C.and the solution was allowed to stand under autogenous pressure at 120°C. for 3 hours.

The product was centrifuged and the supernatant decanted. Theprecipitated product was suspended in about 50 ml ethanol and filteredover a 0.45 μm polypropylene hydrophilic filter using a Büchner funnel.Additional 200 ml ethanol were used to wash the product.

The obtained magnesium hydroxide chloride hydrate nanowires weresuspended in 12 ml ethanol and 2.4 ml deionized water in a 20 ml vial.1.6 ml of 5M NaOH aqueous solution were added and the vial was sealedwith its cap. The mixture was then heated at 65° C. in an oven for 15 h.

The product was filtered over a 0.45 μm polypropylene hydrophilic filterusing a Büchner funnel. About 250 ml ethanol were used to wash theproduct. The obtained Mg(OH)₂ nanowires were dried at 65° C. for 15 h inan oven. Finally, the dried product was calcined in a muffle furnaceusing a step recipe (load in the furnace at room temperature, ramp to100° C. with 2° C./min rate, dwell for 60 min, ramp to 280° C. with 2°C./min rate, dwell for 60 min, ramp to 350° C. with 2° C./min rate,dwell for 60 min, ramp to 450° C. with 2° C./min rate, dwell for 60 min,cool to room temperature) to convert it to MgO nanowires.

Example 28 Synthesis of Mg(OH)₂ Nanowires

6.8 g of MgCl₂.6H₂O were dissolved in 5 ml deionized water in a 20 mlvial. 0.4 g of MgO (from Aldrich) were then slowly added to the solutionwhile it was vigorously stirred. The mixture was kept stirring at roomtemperature until it completely jellified (˜2 h) and then it was leftaging for 48 h without stirring.

The gel was transferred in a 50 ml centrifuge tube, which was thenfilled with deionized water and vigorously shaken until a homogenoussuspension was obtained. The suspension was centrifuged and thesupernatant decanted. The precipitated product was suspended in about 50ml ethanol and filtered over a 0.45 μm polypropylene hydrophilic filterusing a Büchner funnel. Additional 350 ml ethanol were used to wash theproduct.

The obtained magnesium hydroxide chloride hydrate nanowires weresuspended in 24 ml ethanol in a 50 ml media bottle. The mixture wasstirred for a few minutes, then 4.8 ml deionized water and 3.2 ml of 5MNaOH aqueous solution were added. The media bottle was sealed with itscap and the mixture was stirred for few more minutes. The mixture wasthen heated at 65° C. in an oven for 15 h.

The product was filtered over a 0.45 μm polypropylene hydrophilic filterusing a Büchner funnel. About 400 ml ethanol were used to wash theproduct. The obtained Mg(OH)₂ nanowires were dried at 65° C. for 72 h inan oven and then additionally dried at 120° C. for 2 h in a vacuum oven.About 0.697 g of Mg(OH)₂ nanowires were obtained and the surface area ofthe nanowires was determined by BET (Brunauer, Emmett, Teller)measurement at 100.4 m²/g.

Example 29 Synthesis of MnO/Mn₂O₃ Core/Shell Nanowires

This example describes a method for coating the Mg(OH)₂ nanowires fromexample 28 with MnO(OH).

Three almost identical syntheses were conducted in parallel. In eachsynthesis, the Mg(OH)₂ nanowires, prepared using the method described inexample 28 but without the drying steps, were mixed with 250 mldeionized water in a 500 ml plastic bottle and stirred for 20 minutes.2.4 ml of a 1M MnCl₂ solution were added to the first synthesis, 6 ml ofa 1M MnCl₂ solution were added to the second synthesis and 9.6 ml of a1M MnCl₂ solution were added to the third synthesis. The mixtures werestirred for 2 hours at room temperature. After this incubation period, aslow multistep addition was conducted with 1.2 ml, 3 ml and 4.8 ml of0.1 M LiOH solution for the first, second and third synthesis,respectively. This addition was conducted in 2 hours and 20 steps. Thereaction mixture was left stirred overnight (˜15 h) at room temperature.After that time the suspensions were centrifuged in order to separatethe solid phase from the liquid phase. The precipitated materials werethen re-suspended in 50 ml of ethanol for each synthesis and filteredover a 0.45 μM polypropylene hydrophilic filter using a Büchner funnel.Additional 350 ml ethanol were used to wash each product of the threesynthesis.

The obtained Mg(OH)₂/MnO(OH) core/shell nanowires were characterized byTEM before being dried at 65° C. for 72 h in an oven and thenadditionally dried at 120° C. for 2 h in a vacuum oven. The yield forthe three syntheses was 0.675 g, 0.653 g and 0.688 g, respectively. Thesurface area of the nanowires was determined by BET (Brunauer, Emmett,Teller) measurement at 94.6 m²/g, 108.8 m²/g and 108.7 m²/g,respectively.

The Mg(OH)₂/MnO(OH) core/shell nanowires can be converted into MgO/Mn₂O₃nanowires by calcining them in a muffle furnace using a step recipe(load in the furnace at room temperature, ramp to 100° C. with 2° C./minrate, dwell for 60 min, ramp to 280° C. with 2° C./min rate, dwell for60 min, ramp to 350° C. with 2° C./min rate, dwell for 60 min, ramp to450° C. with 2° C./min rate, dwell for 60 min, ramp to 550° C. with 2°C./min rate, dwell for 60 min, cool to room temperature).

Example 30 Preparation of Nd₂O₃, Eu₂O₃ and Pr₂O₃ Nanowires

Three syntheses were made in parallel. In each synthesis, 10 ml of a 2.5e12 pfu/ml solution of phage (SEQ ID NO: 14) were mixed in a 60 ml glassvial with 25 μl of 0.08M NdCl₃, EuCl₃ or PrCl₃ aqueous solutions,respectively and left incubating for at least 1 hour. After thisincubation period, a slow multistep addition was conducted with 630 μlof 0.08M LaCl₃, EuCl₃ or PrCl₃ aqueous solutions, respectively and 500μl of 0.3M NH4OH. This addition was conducted in 33 hours and 60 steps.The reaction mixtures were left stirred for at least another 10 hour atroom temperature. After that time the suspensions were centrifuged inorder to separate the solid phase from the liquid phase. Theprecipitated material was then re-suspended in 4 ml of ethanol. Theethanol suspensions were centrifuged in order to finish removingun-reacted species. The gel-like product remaining was then dried for 1hours at 65° C. in an oven and then calcined in a muffle oven in air(load in the furnace at room temperature, ramp to 100° C. with 2° C./minrate, dwell for 30 min, ramp to 500° C. with 2° C./min rate, dwell for240 min, cool to room temperature). The obtained Nd(OH)₃, Eu(OH)₃ andPr(OH)₃ nanowires were characterized by TEM before being dried.

Example 31 Preparation of Ce₂O₃/La₂O₃ Mixed Oxide Nanowires

In the synthesis, 15 ml of a 5 e12 pfu/ml solution of phage (SEQ ID NO:3) were mixed in a 60 ml glass vial with 15 μl of 0.1M La(NO₃)₃ aqueoussolution and left incubating for about 16 hour. After this incubationperiod, a slow multistep addition was conducted with 550 μl of 0.2MCe(NO₃)₃ aqueous solution, 950 μl of 0.2M La(NO₃)₃ aqueous solution and1500 μl of 0.4M NH₄OH. This addition was conducted in 39 hours and 60steps. The reaction mixtures were left stirred for at least another 10hours at room temperature. After that time the suspensions werecentrifuged in order to separate the solid phase from the liquid phase.The precipitated material was then re-suspended in 4 ml of ethanol. Theethanol suspensions were centrifuged in order to finish removingun-reacted species. The gel-like product remaining was then dried for 1hours at 65° C. in an oven and then calcined in a muffle oven in air(load in the furnace at room temperature, ramp to 100° C. with 2° C./minrate, dwell for 30 min, ramp to 500° C. with 2° C./min rate, dwell for120 min, cool to room temperature).

Example 32 Synthesis of Pr₂O₃/La₂O₃ Mixed Oxide Nanowires

0.5 ml of 1M Pr(NO₃)₃ aqueous solution and 4.5 ml of 1M La(NO₃)₃ aqueoussolution were mixed with 40 ml deionized water. Once well mixed, 5 ml ofa 3M NH₄OH aqueous solution were quickly injected in the mixture. Aprecipitate immediately formed. The suspension was kept stirring foranother 10 minutes then transferred to centrifuge tubes and centrifugedin order to separate the solid phase from the liquid phase. Theprecipitated material was then re-suspended in 35 ml of deionized water.The solid fraction was separated again by centrifugation and the washingstep was repeated one more time. The gel-like product remaining was thendispersed in deionized water and the suspension volume adjusted to 20ml. The suspension was then transferred to a hydrothermal bomb andplaced in an oven at 120° C. for 2 hours. The solids obtained afterhydrothermal treatment were then separated by centrifugation and washedonce with 35 ml of deionized water. The washed hydrothermally treatedpowder was then dried at 120° C. for 16 hours. The surface area,determine by BET, of the dried powder was about 41 m²/g. Transmissionelectron microscopy was used to characterize the morphology of thissample further. The powder was constituted of large aspect ratioparticles with about 30 nm wide by 0.5 to 2 μm length. The powder wascalcined in three temperature steps at 200, 400 and 500° C. with 3°C./min ramp and 2 hours of dwell time at each step. The surface area ofthe Pr₂O₃/La₂O₃ mixed oxide nanowires was about 36 m²/g.

Example 33 Synthesis of MgO/Eu₂O₃ Core/Shell Nanowires

In this example, Mg(OH)₂ nanowires are used as a support to grow a shellof Eu(OH)₃. Mg(OH)₂ nanowires, prepared according to the methodsdescribed in example 28 (wet product, before being dried) were used toprepare a suspension in deionized water with a concentration of 3 g/l ofdried Mg(OH)₂. To 30 ml of the Mg(OH)₂ suspension, 3 ml of 0.1M Eu(NO₃)₃aqueous solution and 3 ml of 0.3M NH₄OH aqueous solution were added in aslow multistep addition. This addition was conducted in 48 hours and 360steps. The solids were then separated using centrifugation. The powderis washed with 30 ml DI water and centrifuged again. An aliquot isretrieved prior to calcination for transmission electron miscopyevaluation of the sample morphology. The sample is mainly constituted ofhigh aspect ratio wires with a rough surface. The general morphology ofthe support is preserved and no separate phase is observed.

The remaining of the powder was dried at 120° C. for 3 hours andcalcined in three steps at 200, 400 and 500° C. with 2 hours at eachstep and a ramp rate of 3° C./min. The surface area, determined by BET,of the MgO/Eu₂O₃ core/shell nanowires is 209 m²/g.

Example 34 Synthesis of Y₂O₃/La₂O₃ Mixed Oxide Nanowires

0.5 ml of 1M Y(NO₃)₃ aqueous solution and 4.5 ml of 1M La(NO₃)₃ aqueoussolution were mixed with 40 ml deionized water. Once well mixed, 5 ml ofa 3M NH4OH aqueous solution was quickly injected in the mixture. Aprecipitate immediately forms. The suspension was kept stirring foranother 10 minutes then transferred to centrifuge tubes and centrifugedin order to separate the solid phase from the liquid phase. Theprecipitated material was then re-suspended in 35 ml deionized water.The solid fraction was separated again by centrifugation and the washingstep was repeated one more time. The gel-like product remaining was thendispersed in deionized water and the suspension volume adjusted to 20ml. The suspension was then transferred to a hydrothermal bomb andplaced in an oven at 120° C. for 2 hours. The solids obtained afterhydrothermal treatment were then separated by centrifugation and washedonce with 35 ml of deionized water. The washed hydrothermally treatedpowder was then dried at 120° C. for 16 hours. The surface area,determined by BET, of the dried powder is about 20 m2/g. Transmissionelectron microscopy was used to characterize the morphology of thissample further. The powder was constituted of large aspect ratioparticles with about 20 to 40 nm wide by 0.5 to 2 micron length. TheY₂O₃/La₂O₃ mixed oxide nanowires ware calcined in three temperaturesteps at 200, 400 and 500° C. with 3° C./min ramp and 2 hours of dwelltime at each step.

Example 35 Synthesis of La₂O₃ Nanowires

1 g of La₂O₃ (13.1 mmol) and 0.92 g of NH₄Cl (18.6 mmol) were placed ina 25 ml stainless steel autoclave with a Teflon liner (Parr Bomb No.4749). 10 ml deionized water were then added to the dry reactants. Theautoclave was sealed and placed in a 160° C. oven for 12 h. After 12 h,the autoclave was allowed to cool. The nanowires were washed severaltimes with 10 mL of water to remove any excess NH₄Cl. The product wasthen dried in an oven for 15 hours at 65° C. in an oven and thencalcined in a muffle oven in air (load in the furnace at roomtemperature, ramp to 100° C. with 2° C./min rate, dwell for 30 min, rampto 400° C. with 2° C./min rate, dwell for 240 min, ramp to 550° C. with2° C./min rate, dwell for 240 min, cool to room temperature.)

Example 36 Synthesis of La₂O₃/Nd₂O₃ Mixed Oxide Nanowires

0.5 g of La₂O₃ (1.5 mmol), 0.52 g of Nd₂O₃ (1.5 mmol), and 0.325 g ofNH₄Cl (6 mmol) were ground together using a mortar and pestle. Once thedry reactants were well mixed, the ground powder was placed in a ceramiccrucible and then the crucible was transferred to a tube furnace. Thetube furnace atmosphere was flushed with nitrogen for 0.5 h. Thereactants were then calcined under nitrogen (25° C.-450° C., 2° C./minramp, dwell 1 h; 450° C.-900° C.; 2° C./min ramp, 1 h hold, cool to roomtemperature.) The product (0.2 g) was placed in 10 mL of deionized waterand stirred at room temperature for 24 h. The nanowires were then washedseveral times with deionized H₂O and dried in an oven for 15 hours at65° C. in an oven and then calcined in a muffle oven in air (load in thefurnace at room temperature, ramp to 100° C. with 2° C./min rate, dwellfor 30 min, ramp to 400° C. with 2° C./min rate, dwell for 240 min, rampto 550° C. with 2° C./min rate, dwell for 240 min, cool to roomtemperature.)

Example 37 Oligomerization of Ethylene to Liquid Hydrocarbon Fuels withHigh Aromatics Content

0.1 g of the zeolite ZSM-5 is loaded into a fixed bed micro-reactor andheated at 400° C. for 2 h under nitrogen to activate the catalyst. TheOCM effluent, containing ethylene and ethane, is reacted over thecatalyst at 400° C. at a flow rate of 50 mL/min and GSHV=3000-10000mL/(g h). The reaction products are separated into liquid and gascomponents using a cold trap. The gas and liquid components are analyzedby gas chromatography. C5-C10 hydrocarbon liquid fractions, such asxylene and isomers thereof, represent ≧90% of the liquid product ratiowhile the C11-C15 hydrocarbon fraction represents the remaining 10% ofthe product ratio.

Example 38 Oligomerization of Ethylene to Liquid Hydrocarbon Fuels withHigh Olefins Content

0.1 g of the zeolite ZSM-5 doped with nickel is loaded into a fixed bedmicro-reactor and heated at 350° C. for 2 h under nitrogen to activatethe catalyst. The OCM effluent, containing ethylene and ethane, isreacted over the catalyst at 250-400° C. temperature rage withGSHV=1000-10000 mL/(g h). The reaction products are separated intoliquid and gas components using a cold trap. The gas and liquidcomponents are analyzed by gas chromatography. C₄-C₁₀ olefin hydrocarbonliquid fractions, such as butene, hexane and octene represent ≧95% ofthe liquid product ratio while the C₁₂-C₁₈ hydrocarbon fractionrepresents the remaining 5% of the product ratio. Some trace amounts ofodd numbered olefins are also possible in the product.

Example 39 Synthesis of MnWO₄ Nanowires

0.379 g of Na₂WO₄ (0.001 mol) was dissolved in 5 mL of deionized water.0.197 g of MnCl₂.6H2O (0.001 mol) was dissolved in 2 mL of deionizedwater. The two solutions were then mixed and a precipitate was observedimmediately. The mixture was placed in a stainless steel autoclave witha Teflon liner (Parr Bomb No. 4749). 40 ml of deionized water was addedto the reaction mixture and the pH was adjusted to 9.4 with NH4OH. Theautoclave was sealed and placed in a 120° C. oven. The reaction was leftto react for 18 h and then it was cooled to room temperature. Theproduct was washed with deionized water and then dried in a 65° C. oven.The samples were calcined in a muffle oven in air (load in the furnaceat room temperature, ramp to 400° C. with 5° C./min rate, dwell for 2 h,ramp to 850° C. with 5° C./min rate, dwell for 8 h, cool to roomtemperature).

Example 40 Preparation of Supported MnWO₄ Nanowire Catalysts

Supported MnWO₄ nanowires catalysts are prepared using the followinggeneral protocol. MnWO₄ nanowires are prepared using the methoddescribed in example 42. Manganese tungstate nanowires, support, andwater are slurried for 6 h at room temperature. The manganese tungstateto support ratio is 2-10 wt %. The mixture is dried in a 65° C. oven andthen calcined in a muffle oven in air: load in the furnace at roomtemperature, ramp to 400° C. with 5° C./min rate, dwell for 2 h, ramp to850° C. with 5° C./min rate, dwell for 8 h, cool to room temperature.The following is a list of exemplary supports that may be used: SiO₂,Al₂O₃, SiO₂—Al₂O₃, ZrO₂, TiO₂, HfO₂, Silica-Aluminum Phosphate, andAluminum Phosphate.

Example 41 OCM Catalyzed by La₂O₃ Nanowires

50 mg of La₂O₃ nanowires catalyst, prepared using the method describedin example 19, were placed into a reactor tube (4 mm ID diameter quartztube with a 0.5 mm ID capillary downstream), which was then tested in anAltamira Benchcat 203. The gas flows were held constant at 46 sccmmethane and 54 sccm air, which correspond to a CH4/O2 ratio of 4 and afeed gas-hour space velocity (GHSV) of about 130000/hour. The reactortemperature was varied from 400° C. to 500° C. in a 100° C. incrementand from 500° C. to 850° C. in 50° C. increments. The vent gases wereanalyzed with gas chromatography (GC) at each temperature level.

FIG. 24 shows the onset of OCM between 500° C. and 550° C. The C2selectivity, methane conversion and C2 yield at 650° C. were 54%, 27%and 14%, respectively.

Example 42 Synthesis of La₂O₃ Nanowires

La₂O₃ (3.1 mmol) and NH₄NO₃ (other lanthanides and different ammoniumsalts, e.g., Cl or acetate and the like may also be used) (18.6 mmol)were placed in a stainless steel autoclave with a Teflon liner. Water(10 mL) was then added to the dry reactants. The autoclave was sealedand placed in a 160° C. oven for 12 h. After 12 h, the autoclave wasallowed to cool (the ammonium acetate catalyzed reaction required 48 h).The nanowires were washed several times with 10 mL of water to removeany excess NH₄NO₃. The product was then dried in an oven for 15 hours at65° C. and then calcined in a muffle oven in air (load in the furnace atroom temperature, ramp to 100° C. with 2° C./min rate, dwell for 30 min,ramp to 400° C. with 2° C./min rate, dwell for 240 min, ramp to 550° C.with 2° C./min rate, dwell for 240 min, cool to room temperature.)Nanowire formation was confirmed by TEM. Calcination by microwave mayalso be used.

Example 43 Synthesis of La₂O₃ Nanowires

La₂O₃ (1.02 g), NH₄NO₃ (1.64 g) and 20 mL of deionized water were addedto a round bottom flask equipped with a stir-bar and a reflux condenser.The suspension was refluxed for 18 h. The product was washed with DIwater and dried. The product was then calcined in a muffle ovenaccording to the procedure described in Example 42. Nanowire formationwas confirmed by TEM. Calcination by microwave may also be used.

Example 44 Purification of Bacteriophage M13 by TFF

In this example, both the microfiltration and the ultrafiltration stepswere performed using TFF. A batch of M13 filamentous bacteriophagegenetically engineered to express AEEEDP at the N-terminus of the maturepVIII protein (SEQ ID NO: 3) was amplified by incubation with E. colibacteria. The concentration of the amplified solution was quantified bytitration to be 7.7E11 pfu/mL. 890 mL of the solution was purified usingthe following parameters. For microfiltration, a 0.2 μm nylon flat sheetmembrane cartridge was used. Prior to purification the membrane wascleaned and the normalized water flux was verified to be ≧85% of factoryrating. Flow parameters of 550 L/hr/m² and transmembrane pressure at 15psi were used. Prior to filtration the cell solution was recirculatedfor an hour at the same flow and pressure to equilibrate the membrane.Following this recirculation, the amplification culture was concentratedvia TFF for ˜4 hrs, until the retentate volume was 100 mL (˜10 timesless than original).

The retentate obtained above was diafiltered with approximately 2.5volumes (270 mL) of Tris buffered saline pH 7.5 (TBS). The TBS filtratewas also collected with the permeate solution, containing the phage. Thefinal yield of phage in the permeate was 2.3% as verified by titration(1007 mL at 1.5E10 pfu/mL). For the ultrafiltration and diafiltrationsteps a 100 kD polyethersulfone flat sheet membrane cartridge was used.Prior to purification the membrane was cleaned and the normalized waterflux was verified to be ≧85% of factory rating. The phage solutionclarified through TFF microfiltration as described above was combinedwith another batch similarly prepared. The combination resulted in atotal of 1953 mL of solution of phage at a concentration of 4E9 pfu/mL.Flow parameters of approximately 1640 L/hr/m² and a transmembranepressure of 7 psi were used. The retentate containing the phage productwas concentrated 17 times and diafiltered with 10 volumes of deionizedwater. After sample collection, the system was rinsed through with avolume equivalent to the hold up volume (45 mL). The final yield ofphage in the retentate was ˜100% as verified by titration (113 mL,6.8E10 pfu/mL).

Example 45 Purification of Bacteriophage M13 by Depth Filtration and TFF

In this example, instead of TFF microfiltration, depth filtration wasused for the initial step to clarify the amplification phage (SEQ ID NO:3) culture of bacterial cells, grown similarly as described in Example44, of bacterial cells and cell debris. The second step to filter outmedia components and smaller contaminating bacterial cell particles suchas proteins was performed with TFF ultrafiltration and diafiltration.2660 mL of the amplification culture with an initial phage concentrationof 1.2E12 pfu/mL was purified using the following parameters. Depthfiltration was performed using a path containing two filters, a glassfiber cartridge with a nominal porosity rating of 1.2 μm, followed by afilter with double pleated polyethersulfone membranes, rated at 0.8 μmand 0.45 μm respectively. The filtration was performed at a constantpressure of 7 psi. The yield of phage in the filtrate was 86% (2500 mL1.1E12 pfu/mL). For the ultrafiltration and diafiltration steps a 500 kDpolyethersulfone flat sheet membrane cartridge was used. Prior topurification the membrane was cleaned and the normalized water flux wasverified to be ≧85% of original. 2007 mL of phage purified by depthfiltration above (1.1E12 pfu/mL) was purified. Flow parameters ofapproximately 2200 L/hr/m² and a transmembrane pressure of 7 psi wereused. The solution was concentrated with the TFF 1 hr and 35 min until˜180 mL were remaining in the retentate (˜10× concentration). The phagesolution was then diafiltered with 2000 mL deionized water withrecirculation for approximately one hour. The final volume collected was156 mL at a concentration of 1.4E13 pfu/mL which corresponds to ˜98% ofstarting phage material.

Example 46 Preparation of Catalytic Material Comprising CordieriteHoneycomb Ceramic Supported Nd₂O₃ Nanowires

Nd₂O₃ nanowires were prepared in a manner analogous to Example 14 bysubstituting La(NO₃)₃ with Nd(NO₃)₃.

A 400 mg aliquot of Nd₂O₃ nanowires is mixed with 2 g of DI water andplaced into a 5 ml glass vial containing 2 mm Yttria Stabilized Zirconiamilling balls. The vial is placed on a shaker at 2000 RPM and agitatedfor 30 minutes. A thick slurry is obtained.

A ⅜ inch diameter core is cut along the channel direction into a 400CPSI (channel per square inch) cordierite honeycomb monolith and cut inlength so the core volume is approximately 1 ml.

The core is placed into a ⅜ inch tube, and the catalyst slurry is fed ontop of the ceramic core and pushed with compressed air through themonolith channel. The excess slurry is captured into a 20 ml vial. Thecoated core is removed from the ⅜ inch tube and placed into a dryingoven at 200° C. for 1 hour.

The coating step is repeated twice more time with the remaining slurryfollowed by drying at 200° C. and calcination at 500° C. for 4 hours.The catalyst amount deposited on the monolith channel walls isapproximatively 50 mg and comprises very good adhesion to the ceramicwall.

Example 47 Preparation of Catalytic Material Comprising Silicon CarbideCeramic Foam Supported Nd₂O₃ Nanowires

Nd₂O₃ nanowires were prepared in a manner analogous to Example 14 bysubstituting La(NO₃)₃ with Nd(NO₃)₃.

A 400 mg aliquot of Nd₂O₃ nanowires is mixed with 2 g of DI water andplaced into a 5 ml glass vial containing 2 mm Yttria Stabilized Zirconiamilling balls. The vial is placed on a shaker at 2000 RPM and agitatedfor 30 minutes. A thick slurry is obtained.

A ⅜ inch diameter core is cut from a 65 PPI (Pore Per Inch) SiC foam andcut in length so the core volume is approximately 1 ml.

The core is placed into a ⅜ inch tube and the catalyst slurry is fed ontop of the ceramic core and pushed with compressed air through themonolith channel. The excess slurry is captured into a 20 ml vial. Thecoated core is removed from the ⅜ inch tube and placed into a dryingoven at 200° C. for 1 hour.

The coating step is repeated twice more time with the remaining slurryfollowed by drying at 200° C. and calcination at 500° C. for 4 hours.The catalyst amount deposited on the monolith channel walls isapproximatively 60 mg and comprises very good adhesion to the ceramicmesh.

Example 48 Preparation of Catalytic Material Comprising Silicon Carbideand Nd₂O₃ Nanowires

Nd₂O₃ nanowires were prepared in a manner analogous to Example 14 bysubstituting La(NO₃)₃ with Nd(NO₃)₃.

A 400 mg aliquot of Nd₂O₃ nanowires is dry blend mixed with 400 mg of200-250 mesh SiC particles for 10 minutes or until the mixture appearshomogeneous and wire clusters are no longer visible. The mixture is thenplaced into a ¼ inch die and pressed in 200 mg batches. The pressedpellets are then placed into an oven and calcined at 600° C. for 2hours. The crush strength of the pellet obtained is comparable to thecrush strength of a pellet made with only Nd₂O₃ nanowires.

Example 49 OCM Activity of Various Nanowire Catalysts

Exemplary nanowire catalysts comprising La₂O₃, Nd₂O₃ or La₃NdO₆ withone, two, three or four different dopants selected from Eu, Na, Sr, Ho,Tm, Zr, Ca, Mg, Sm, W, La, K, Ba, Zn, and Li, were prepared and testedfor their OCM activity according to the general procedures described inthe above examples. Each of the exemplary catalysts produced a C2 yieldabove 10%, a C2 selectivity above 50%, and a CH₄ conversion above 20%,when tested as OCM catalysts at 650° C. or lower at pressures rangingfrom 1 to 10 atm.

Example 50 Preparation of Sr Doped La₂O₃ Nanowires

Sr doped La₂O₃ nanowires are prepared according to the following method.

A 57 mg aliquot of La₂O₃ nanowires prepared as described herein is thenmixed with 0.174 ml of a 0.1 M solution of Sr(NO₃)₂. This mixture isthen stirred on a hot plate at 90° C. until a paste was formed.

The paste is then dried for 1 h at 120° C. in a vacuum oven and finallycalcined in a muffle oven in air according to the following procedure:(1) load in the furnace at room temperature; (2) ramp to 200° C. with 3°C./min rate; (3) dwell for 120 min; (3) ramp to 400° C. with 3° C./minrate; (4) dwell for 120 min; (5) ramp to 500° C. with 3° C./min rate;and (6) dwell for 120 min. The calcined product is then ground to a finepowder.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet, areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments. These and other changes can be made to the embodiments inlight of the above-detailed description. In general, in the followingclaims, the terms used should not be construed to limit the claims tothe specific embodiments disclosed in the specification and the claims,but should be construed to include all possible embodiments along withthe full scope of equivalents to which such claims are entitled.Accordingly, the claims are not limited by the disclosure.

The invention claimed is:
 1. A method for the preparation of ethane,ethylene or combinations thereof, the method comprising contacting acatalytic material with a gas comprising methane, wherein the catalyticmaterial is in the form of a pressed pellet, extrudate or monolith andcomprises: a) a plurality of catalytic nanowires, the catalyticnanowires comprising one or more doping elements; and b) a diluent orsupport selected from one or more alkaline earth metal compounds, andwherein the catalytic material has a C2+ yield above 5% when employed ascatalytic material in the oxidative coupling of methane at an inlettemperature of 550° C. and an inlet pressure of about 2 atm in a fixedbed reactor with a gas-hour space velocity (GHSV) of at least about20,000/hr.
 2. The method of claim 1, wherein the catalytic materials isin the form of a pressure treated, pressed pellet and comprises nobinder material.
 3. The method of claim 1, wherein the catalyticmaterial is in the form of a pressed pellet or extrudate and comprisespores greater than 20 nm in diameter.
 4. The method of claim 1, whereinthe alkaline earth metal compound is an alkaline earth metal oxide,alkaline earth metal carbonate, alkaline earth metal sulfate or alkalineearth metal phosphate.
 5. The method of claim 1, wherein the alkalineearth metal compound is an alkaline earth metal carbonate, alkalineearth metal sulfate or alkaline earth metal phosphate.
 6. The method ofclaim 1, wherein the alkaline earth metal compound is MgO, MgCO₃, MgSO₄,Mg₃(PO₄)₂, MgAl₂O₄, CaO, CaCO₃, CaSO₄, Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃,SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄, BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ orcombinations thereof.
 7. The method of claim 1, wherein the alkalineearth metal compound is MgCO₃, MgSO₄, Mg₃(PO₄)₂, CaO, CaCO₃, CaSO₄,Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄, BaO, BaCO₃,BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ or combinations thereof.
 8. The method ofclaim 1, wherein the alkaline earth metal compound is CaO, SrO, MgCO₃,CaCO₃, SrCO₃ or combinations thereof.
 9. The method of claim 1, whereinthe plurality of catalytic nanowires have a ratio of average effectivelength to average actual length of less than one and an average aspectratio of greater than ten as measured by TEM in bright field mode at 5keV, wherein the plurality of catalytic nanowires comprises one or moreelements from any of Groups 1 through 7, lanthanides, actinides orcombinations thereof.
 10. The method of claim 1, wherein the pluralityof catalytic nanowires comprises straight nanowires.
 11. The method ofclaim 10, wherein the straight nanowires have a ratio of effectivelength to actual length equal to one.
 12. The method of claim 1, whereinthe plurality of catalytic nanowires comprises at least one nanowireselected from any one of Tables 1-12.
 13. The method of claim 1, whereinthe catalytic material has a C2 selectivity above 50% when employed ascatalytic material in the oxidative coupling of methane at an inlettemperature of 550° C. and an inlet pressure of about 2 atm in a fixedbed reactor with a gas-hour space velocity (GHSV) of at least about20,000/hr.
 14. The method of claim 1, wherein the catalytic material hasa CH₄ conversion above 20% when employed as catalytic material in theoxidative coupling of methane at an inlet temperature of 550° C. and aninlet pressure of about 2 atm in a fixed bed reactor with a gas-hourspace velocity (GHSV) of at least about 20,000/hr.
 15. The method ofclaim 1, wherein the catalytic material further comprises SiC orcordierite or combinations thereof.
 16. The method of claim 1, whereinthe catalytic material is contacted with the gas at a temperature lessthan 800° C.
 17. The method of claim 1, wherein the catalytic materialis contacted with the gas at a temperature less than 700° C.
 18. Themethod of claim 1, having a conversion of methane to ethylene of greaterthan 10%.
 19. The method of claim 1, having a yield of ethylene ofgreater than 10%.
 20. The method of claim 1, having a conversion ofmethane of greater than 10%.
 21. The method of claim 1, having a C2yield of greater than 10%.
 22. The method of claim 2, wherein theplurality of catalytic nanowires have a ratio of average effectivelength to average actual length of less than one and an average aspectratio of greater than ten as measured by TEM in bright field mode at 5keV, wherein the plurality of catalytic nanowires comprises one or moreelements from any of Groups 1 through 7, lanthanides, actinides orcombinations thereof.
 23. The method of claim 2, wherein the pluralityof catalytic nanowires comprises straight nanowires.
 24. The method ofclaim 23, wherein the straight nanowires have a ratio of effectivelength to actual length equal to one.
 25. The method of claim 2, whereinthe plurality of catalytic nanowires comprises at least one nanowireselected from any one of Tables 1-12.
 26. The method of claim 2, whereinthe alkaline earth metal compound is an alkaline earth metal oxide,alkaline earth metal carbonate, alkaline earth metal sulfate or alkalineearth metal phosphate.
 27. The method of claim 2, wherein the alkalineearth metal compound is MgO, MgCO₃, MgSO₄, Mg₃(PO₄)₂, MgAl₂O₄, CaO,CaCO₃, CaSO₄, Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄,BaO, BaCO₃, BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ or combinations thereof.
 28. Themethod of claim 2, wherein the alkaline earth metal compound is MgO,CaO, SrO, MgCO₃, CaCO₃, SrCO₃ or combinations thereof.
 29. The method ofclaim 2, wherein the catalytic material has a C2 selectivity above 50%when employed as catalytic material in the oxidative coupling of methaneat an inlet temperature of 550° C. and an inlet pressure of about 2 atmin a fixed bed reactor with a gas-hour space velocity (GHSV) of at leastabout 20,000/hr.
 30. The method of claim 2, wherein the catalyticmaterial has a CH₄ conversion above 20% when employed as catalyticmaterial in the oxidative coupling of methane at an inlet temperature of550° C. and an inlet pressure of about 2 atm in a fixed bed reactor witha gas-hour space velocity (GHSV) of at least about 20,000/hr.
 31. Themethod of claim 2, wherein the catalytic material further comprises SiCor cordierite or combinations thereof.
 32. The method of claim 3,wherein the plurality of catalytic nanowires have a ratio of averageeffective length to average actual length of less than one and anaverage aspect ratio of greater than ten as measured by TEM in brightfield mode at 5 keV, wherein the plurality of catalytic nanowirescomprises one or more elements from any of Groups 1 through 7,lanthanides, actinides or combinations thereof.
 33. The method of claim3, wherein the plurality of catalytic nanowires comprises straightnanowires.
 34. The method of claim 33, wherein the straight nanowireshave a ratio of effective length to actual length equal to one.
 35. Themethod of claim 3, wherein the plurality of catalytic nanowirescomprises at least one nanowire selected from any one of Tables 1-12.36. The method of claim 3, wherein the catalytic material has a C2selectivity above 50% when employed as catalytic material in theoxidative coupling of methane at an inlet temperature of 550° C. and aninlet pressure of about 2 atm in a fixed bed reactor with a gas-hourspace velocity (GHSV) of at least about 20,000/hr.
 37. The method ofclaim 3, wherein the catalytic material has a CH₄ conversion above 20%when employed as catalytic material in the oxidative coupling of methaneat an inlet temperature of 550° C. and an inlet pressure of about 2 atmin a fixed bed reactor with a gas-hour space velocity (GHSV) of at leastabout 20,000/hr.
 38. The method of claim 3, wherein the alkaline earthmetal compound is an alkaline earth metal oxide, alkaline earth metalcarbonate, alkaline earth metal sulfate or alkaline earth metalphosphate.
 39. The method of claim 3, wherein the alkaline earth metalcompound is MgO, MgCO₃, MgSO₄, Mg₃(PO₄)₂, MgAl₂O₄, CaO, CaCO₃, CaSO₄,Ca₃(PO₄)₂, CaAl₂O₄, SrO, SrCO₃, SrSO₄, Sr₃(PO₄)₂, SrAl₂O₄, BaO, BaCO₃,BaSO₄, Ba₃(PO₄)₂, BaAl₂O₄ or combinations thereof.
 40. The method ofclaim 3, wherein the alkaline earth metal compound is MgO, CaO, SrO,MgCO₃, CaCO₃, SrCO₃ or combinations thereof.
 41. The method of claim 3,wherein the catalytic material further comprises SiC or cordierite orcombinations thereof.